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IB Chemistry HL Notes
IB Chemistry HL Notes
Yifan Chen
© 2017 NFLS Tutoring Club
Table of Contents
Topic 1: Stoichiometric relationships........................................................................................................................................... 3
Topic 13: The periodic table --- the transition metals (HL) ........................................................................................................ 18
State of matter
Particles vibrate in a fixed Particles move around(vibrate, Particles move around freely,
position rotate, translate) much faster than a liquid
Moles
A mole (mol) of a substance (atoms / molecules / ions):
• contains as many elementary entities (particles, atoms, molecules etc.) as there are atoms in 12 grams of pure carbon-12
• is the relative atomic (or molecular or formula) mass expressed in grams
• 6.02 × 1023elementary entities (Avogadro’s constant)
3
Molar mass
The molar mass (g mol-1) is the mass in grams of one mole of a substance.
Number of particles = number of moles × Avogadro’s constant
Relative abundance
Isotopes are atoms of the same element that have the same number of protons in the nucleus but different numbers of neutrons.
Relative abundance 1 × atomic mass 1 + Relative abundance 2 × atomic mass 2 = Relative atomic mass of this substance
Relative mass
Definitions
Relative atomic mass (Ar) – the relative atomic mass is the average mass of an atom, taking into account the relative
abundances of all the naturally occurring isotopes of the element, relative to one atom of C-12. It is a relative term so it has no
units.
Relative molecular mass (Mr)–the relative molecular mass is the average mass of a molecule, calculated by adding the relative
atomic masses of its constituent atoms. It is a relative term so it has no units.
For formula units (the single units of ionic compounds), the term relative formula mass is used. The mass of a mole of a species is the relative
mass expressed in grams. The number of moles is given by:
Mass (g)
Moles (mol) =
Molar mass (g mol−1 )
Formulas
The molecular formula is the chemical formula of a substance showing the actual number of atoms of each element in a molecule. The
empirical formula is the formula in which the ratio is simplified into the smallest integers.
Problem solving
Experimental Analysis
• Qualitative analysis: determine which elements are in the compound, verify the purity of the compound
• Quantitative analysis: relative mass of elements, work out exact composition
Theoretical yield
Theoretical yields assume that the limiting reagent is 100% used up. The actual yield is called the experimental yield.
experimental yield
Percentage yield (%) = × 100%
theoretical yield
Percentage Purity
Limiting reagent as a means of controlling the amount of product obtained, will be completely consumed during the experiment. Limiting reagents determines
amount of products produced
Problem solving
If A + B → C
1. Calculate how much of reactant B (in moles) is needed to react with the amount of reactant A provided.
2. If the amount needed is less than that provided, B is in excess and vice versa. A is therefore the limiting reagent.
3. The difference between the amount of B needed and the amount of B provided is equivalent to the moles of excess B.
4. The amount of product formed if A reacts completely is the theoretical yield.
Avogadro’s law
Avogadro’s law states that equal volumes of all gases under identical conditions of pressure and temperature contain the same number of
molecules i.e. the molar volume of gas A is the same as that of gas B if the conditions (pressure and temperature) are the same. Under STP
conditions (273K and 1.013 × 105 Pa or 1 atm) the volume per mole is 22.7 dm3. (STP)
Ideal gases
The ideal gas equation is:
𝑃𝑃𝑃𝑃 = 𝑛𝑛𝑛𝑛𝑛𝑛
-1 -1
Where R is the gas constant which has a value of 8.31 J K mol
The ideal gas equation implies Avogadro’s law. We can also use it to derive laws for specific cases by moving the variables to the left hand side
and the constants to the right hand side.
5
𝑃𝑃 𝑃𝑃1 𝑃𝑃2
Gay-Lussac’s law = 𝑘𝑘 =
𝑇𝑇 𝑇𝑇1 𝑇𝑇2
𝑉𝑉 𝑉𝑉1 𝑉𝑉2
Charles’s law = 𝑘𝑘 =
𝑇𝑇 𝑇𝑇1 𝑇𝑇2
Definitions
Molarity – is the concentration of the solution in terms of mol/L Unit: mol dm-3
STP Condition
273K, 1.01× 105Pa ---- 22.7 dm3/mol
6
Topic 2: Atomic structure
2.1 The nuclear atom
U1 Atoms contain a positively charged dense nucleus composed of protons and neutrons (nucleons).
U2 Negatively charged electrons occupy the space outside the nucleus.
U3 The mass spectrometer is used to determine the relative atomic mass of an element from its isotopic composition.
A1 Use of the nuclear symbol notation to deduce the number of protons, neutrons and electrons in atoms and ions.
A2 Calculations involving non-integer relative atomic masses and abundance of isotopes from given data, including mass spectra.
Atomic structure
Protons and neutrons (nucleons) are found in the nucleus. Electrons are found in energy levels or ‘shells’ surrounding the nucleus.
IB definitions
Mass number (A) – the mass number of an atom is the total number of protons plus neutrons in its nucleus.
Atomic number (Z) – the atomic number of an atom is the number of protons in its nucleus. It is also equal to the number of
electrons it contains. The atomic number defines the element and its position in the Periodic Table.
Isotopes – atoms of the same element (and so have the same atomic number, Z) but have different numbers of neutrons (and so
have different mass number, A).
Calculations
• Number of protons = atomic number
• Number of electrons = atomic number – charge e.g. O-2→ 8 – (-2) = 10 electrons
• Number of neutrons = mass number – atomic number
Properties of isotopes
Isotopes show the same chemical properties as neutrons do not participate in chemical reactions. A larger relative atomic mass means a larger
density and a slower movement of atoms for a given temperature. These differences affect the melting and boiling points and can be used in
separation of isotopes
Uses of radioisotopes
Uses of radioisotopes include: nuclear power generation, the sterilisation of surgical instruments in hospitals, crime detection, finding cracks and
stresses in metals and the preservation of food, specifically:
• Carbon-14 is used in carbon-dating.
• Cobalt-60 is used in radiotherapy.(treat cancer)
• Iodine-131 is used as a tracer in medicine for treating and diagnosing illnesses
• Uranium-235 is used for nuclear fission in power plants.
7
The mass spectrometer
A mass spectrometer is used to determine relative atomic masses. (Work under a vacuum)
The stages of operation are:
1. Vaporisation: a vaporised sample is injected into the instrument; this
allows individual atoms to be analysed
2. Ionisation: atoms are bombarded with a stream of high energy electrons,
knocking off valence electrons, generating positively charged species
X(g) + e- ---- X+(g) + 2e-
Calculating the Ar
Using a mass spectrum, we can find out the relative atomic mass. The relative atomic mass is equal to the sum of the relative abundances
multiplied by their respective masses divided by the sum of the relative abundances (which should be 100 if you’re dealing with percentages):
Problems on this subject are usually quite easy; however there is one case which is not immediately obvious: working out the abundances of
isotopes given that there are only two and that you know the Ar. The trick is that if one isotope has an abundance x, then the other must have an
abundance of 100 – x, thus there is only one variable so the problem is capable of being solved.
Problem solving
Chlorine has two isotopes – 35Cl and 37Cl and a relative atomic mass of 35.5. What are the abundances of the two isotopes?
Let x represent the abundance of 35Cl.
𝑥𝑥 × 35 + (100 − 𝑥𝑥) × 37
35.5 =
100
35.5 × 100 = 35𝑥𝑥 + 3700 − 37𝑥𝑥
2𝑥𝑥 = 150
𝑥𝑥 = 75%
Students should be able to identify the ultraviolet, visible and infrared and variation of wavelength and frequency across the spectrum:
A continuous spectrum shows an unbroken sequence of frequencies, such as thespectrum of visible light.A line spectrum is an emission
spectrum that has only certain frequencies of light. It is produced by excited atoms and ions as they fall back to a lower energy level
Energy of eletromagnetic radiation is inversely proportional to wavelength and proportional to
frequency of the radiation.
Planck’s Equation: E = h × f (h – Planck Constant = 6.634 × 10-34Js)
c
f = (λ —wavelength)
λ
700nm 400nm
1
𝐸𝐸 = −𝑅𝑅𝐻𝐻 ( )
𝑛𝑛2
1 1 ℎ𝑐𝑐
Energy of dexicitation of an electron𝛥𝛥𝛥𝛥 = 𝑅𝑅𝐻𝐻 �𝑛𝑛 2 − 𝑛𝑛 2 � = ℎ𝑣𝑣 = 𝜆𝜆
𝑖𝑖 𝑓𝑓
The observed emission spectrum show above results from the energy differences between energy
levels that correspond to frequencies in the visible light region (the Balmer series). These are
jumps from higher energy levels to the second energy levels. Jumps to the first energy level (the
ground state) produce higher frequency emissions (ultraviolet) and jumps down to the third level
produce lower frequency infrared radiation. The lines converge at higher energies because the
energy levels inside the atoms become closer together.
Only electrons in Balmer series can be capture within the visible light range (Electrons coming back to n=2
energy level)
9
Relationships between lines in emission spectrum of hydrogen
As shown in the emission spectrum, lines towards violet colour are getting closer and closer. Also there are only certain distinct lines in the spectrum. So we
can conclude that energy levels inside the atom are discrete and certain, and energy level are getting closer and closer to together as they become more
energetic (e.g. n=4 and n=3 is closer than n=3 and n=2)
2n2Rule
Maximum number of electrons in a given energy level = 2n2
Filling up electrons
Pauli’s Exclusion Principle
No more than two electrons can occupy any one orbital and if two electrons are in the same orbital
they must spin in opposite directions
Aufbau Principle
Electrons are placed into orbitals of lowest energy first (n+l -- energy)
10
Lower n+l value orbital will be filled first
Removing electrons
Removing electrons always is from outermost electrons.
There are two exceptions: (they will then have half filled (or full filled) 3d orbitals --- more stable)
1. Chromium: [Ar]3d54s1[1s22s22p63s23p64s13d5]
Shielding effect
Inner electrons act as shield to block the charge form nucleus. So outermost electrons don’t receive all the forces from the nucleus.
• Distances have more effect than charges, that why as we go down the group, first ionisation energy gets smaller
Effective charges
Effective charges show the effective forces on the electrons. Larger Zeff means stronger forces which the electrons experienced.
Effective charges (Zeff) are depended on numbers of protons and amount of shielding effects. More protons and weaker shielding effect will lead to
large Zeff
11
first ionisation energy for the first twenty elements
2500 Ne
He
• In a group: from top to bottom, first ionisation energy decreases (more shielding effect, electrons are further away from the nucleus
– Zeff decrease)
• In a period: generally increase in the period (more protons but same shielding effect – Zeff increases)
• HOWEVER, there is a decrease from group 2 to group 3 (e.g. Boron has smaller 1stIE value than beryllium); that is because that
electrons are taken from the p orbitals, which is further from nucleus than s orbitals (remember, distance always have most effect)
• Group 5 elements (e.g. nitrogen and phosphorus) have much higher 1st IE value because they have half-filled p-shell, half filled
shell is more stable.
1 2 3 4 5 6 7 8 9 10 11 12 13
ionisation number
Example
Question: Calculate the first ionisation energy in KJ mol-1, for hydrogen given that its shortest-wavelength line in the Lyman series
is 91.16nm.
Converted in to KJ mol-1IE = 2.719 × 10−18 J × 6.022 × 1023 = 1.312 × 106 Jmol−1 = 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝐦𝐦𝐦𝐦𝐦𝐦−𝟏𝟏
12
Topic 3: Periodicity
3.1 The periodic table
U1 The periodic table is arranged into four blocks associated with the four sublevels—s, p, d, and f.
U2 The periodic table consists of groups (vertical columns) and periods (horizontal rows).
U3 The period number (n) is the outer energy level that is occupied by electrons.
U4 The number of the principal energy level and the number of the valence electrons in an atom can be deduced from its position on the periodic table
U5 The periodic table shows the positions of metals, non-metals and metalloids.
A1 Deduction of the electron configuration of an atom from the element’s position on the periodic table, and vice versa.
The elements are arranged in the periodic table in increasing order of atomic mass from left to right. Going down one row increase the number of
electron shells by one. Going one column to the right increases atomic mass by 1.
Group - a group is a vertical column of elements in the Periodic Table. The atoms of the elements in the group all have the same outer shell
structure but an increasing number of inner shells.
Period – a period is a horizontal row of elements in the Periodic Table. Within a period, the atoms of the elements have the same number of
shells but with an increasing number of electrons in the outer shell.
IB definitions
First ionisation energy – the first ionization energy is the minimum energy required to remove a mole of electrons from a mole of
gaseous atoms to form a mole of univalent cations in the gaseous state.
X(g) → X + (g) + e−
Electronegativity – ability of an atom to attract electrons towards itself (man-made scale from 4.0 to 0)
13
Electron Affinity – energy released when one mole of electrons is added to one mole of gas atoms
Atomic Radius
The atomic radius is defined as the distance from the nucleus to the outermost electron or, in practice, half the distance between two bonded
nuclei.
• In a period: atomic size decreasing, as larger Zeff (same amount of shielding but more proton numbers)
• In a group: from top to bottom, the atom size increases (adding more energy level, so the amount of shielding increases, so Zeff decreases)
Ionic Radius
• Positive ion’ radius is smaller than its atom: losing an electron means less outermost electrons, larger forces experienced by each
outermost electrons (effective nuclear charges increase), so the radius gets smaller.
• Negative ion’ radius is larger than its atom: gaining an electron means more outermost electrons, smaller forces experienced by each
outermost electrons (effective nuclear charges decrease), so the radius gets larger
Electron Affinity
Value of electron affinity is negative because energy is released (-ve), not represents magnitude
• From period 2 to period 3, electron affinity increases: putting electrons in n=2 shell (maximum hold 8 electrons), electrons will face relatively larger
repulsion, so it needs more energy to hold the electrons in place, that means less energy will be released. However, in the case of n=3 shell (maximum
hold 18 electrons), there is more space for electrons to move, so it takes relatively less energy to hold the electrons in place, that means more energy
will be released. (inter electron repulsion)
• Group 17 have largest electron affinity value: outer energy level will be fulfilled, so F- will be more stable than F, releasing a lot of energy
• Electron affinity is opposite from first ionisation energy
• In a period: Electron affinity generally increases (more protons but same shielding, larger Zeff, larger attraction to electrons) However, for example
nitrogen has no EA value, because nitrogen itself is stable(half-filled orbitals); Beryllium also doesn’t have EA value, because adding an electron in will
create a new 2p orbitals for beryllium, the distance from the nucleus and more electron shielding makes it very energy-consuming. Lithium EA value is
larger than boron, that is because electron is added into 2s sub-shell, which is closer to the nucleus than 2p sub-shell. Remember, distance matters
most; so the attraction form the nucleus to electron is far more larger
• In a group, electron affinity generally decreases as Zeff decreases except the case discussed above from period 2 to period 3 which has more space and
less inter electron repulsion.
• Group 18 elements don’t have EA value – they are already stable
Electronegativity
Ability of an atom to attract electrons towards itself
• Electronegativity is all about effective nuclear charge, higher Zeff higher electronegativity
• In a period: electronegativity increases (more protons but same shielding, Zeff increases)
• In a group: from top to bottom, electronegativity decreases (electrons are future form the nucleus and more shielding effect, Zeff decrease)
• Fluorine has highest electronegativity value 4.0 --- least shielding, closer to nucleus
14
Trends across period 3
Trend Explanation
across the period. The same trend is observed with ionic radii
4 5 except because the cations have 1 shell fewer they have a
6
smaller radius.
Na+ 7
Mg2+ The graph shows the Si4+ ion (radius: 42), the Si4- ion also
Al3+ exists with a radius of 271.
Si4+
1 2 3 4 5 6 7 8
group number
P
• From Mg to Al – electrons in p orbitals are of higher
Mg Si S energy and further away from the nucleus, thus
easier to remove
• From P to S – an electron in a doubly occupied
Na Al orbital is repelled by its partner and so is easier to
remove than an electron in a half-filled orbital
S
P
Mg Si
Al
Na
1 2 3 4 5 6 7 8
group number
15
Group 1 – the alkali metals
• they are very reactive metals
• they form ionic compounds with non-metals
• the elements further down the group are more reactive that the higher ones since the valence electron is further from nucleus and has
more shielding
• they react with water to form hydrogen and metal hydroxide alkaline solution
• they react with halogens to form ionic salts
Group 7 - halogens
• they are very reactive non-metals
• reactivity decreases down group
• they form ionic compounds with metals and covalent compounds with other non-metals
• higher halogens can displace lower ones from compounds
Formula of Na2O MgO Al2O3 SiO2 P4O10 (s) SO3 (l) Cl2O7 (l)
oxide (s) (s) (s) (s) P4O6 (s) SO2 (g) Cl2O (g)
Acid-base
basic amphoteric acidic
character
• metal oxides are solid because they have strong ionic bonds and therefore form an ionic lattice
• sulphur dioxide is a macromolecular covalent structure like diamond
• the remaining three are molecular covalent
• ionic compounds conduct best because of the mobile charges in molten or aqueous phase
Period 3 chlorides
Formula of
NaCl MgCl2 AlCl3 / Al2Cl6 SiCl4 PCl5 / PCl3 S2Cl2 Cl2
oxide
Physical state solid solid / gas liquid solid / liquid liquid gas
Oxidation
+1 +2 +3 +4 +5 / +3 +1 0
number
Electrical
conductivity in high poor none
molten state
• the more polar the substance is the better it conducts; ionic compounds conduct well
• the ionic compounds have the strongest forces of attraction and are therefore solid
• the non-metal chlorides have dipole-dipole or van der Waals’ forces (depending on whether the dipoles cancel)
16
• Cl2 is non-polar so the IMFs are weak, therefore it is a gas
Reactions of period 3 chlorides with water
Chlorine reacts in a reversible disproportionation (both reduced and oxidised) reaction, producing hydrochloric acid and chloric(I) acid:
The solution is acidic. This is why chlorine turns damp litmus paper red.
Ionic chlorides split into ions in solution, which get surrounded by water molecules (partially charged oxygen to cation and partially charged
hydrogen to anion). They become hydrated.
NaCl(s) → Na+(aq) + Cl−(aq)
MgCl2 (s) → Mg 2+ (aq) + 2Cl−(aq)
The pH of aqueous magnesium chloride is slightly less than 7 because the Mg2+ ion is polarising.
Aluminium chloride dissociates into ions when added to water:
The aluminium ion has a high charge density due to it having a 3+ charge and a small ionic radius. The ion attracts water molecules which form
dative(or coordinate) bonds with the ion to form an octahedral complex ion, [Al(H2O)6]3+
The hydrated ion is acidic as the Al3+ ion attracts the electrons of the OH bond of the surrounding water molecules, and releases the H+ ion to
form an acidic solution.
In summary:
Formula of
NaCl MgCl2 AlCl3 / Al2Cl6 SiCl4 PCl5 / PCl3 S2Cl2 Cl2
oxide
Acid-base
neutral weakly acidic acidic
character
17
Topic 13: The periodic table --- the transition metals (HL)
13.1 First-row d-block elements
U1 Transition elements have variable oxidation states, form complex ions with ligands, have coloured compounds, and display catalytic and magnetic properties.
U2 Zn is not considered to be a transition element as it does not form ions within complete d-orbitals.
U3 Transition elements show an oxidation state of +2 when the s-electrons are removed.
A1 Explanation of the ability of transition metals to form variable oxidation states from successive ionization energies.
A2 Explanation of the nature of the coordinate bond within a complex ion.
A3 Deduction of the total charge given the formula of the ion and ligands present.
A4 Explanation of the magnetic properties in transition metals in terms of unpaired electrons.
12000
10000
ionisation energy/ kJ mol-1
8000
6000
Calcium
4000
Titanium
2000
0
0 1 2 3 4 5 6
ionisation number
The increase in ionisation energies for titanium is more gradual as the 3d and 4s orbitals are close in energy level. Titanium can exist in +2, +3
and +4 oxidation states, but not +5 because the jump in ionisation energies is too large. Students should know that all transition elements can
show an oxidation number of +2. In addition, they should be familiar with the oxidation numbers of the following: Cr (+3, +6), Mn (+4, +7), Fe (+3)
and Cu (+1).
18
Ligand
IB definitions
Ligand – an ion or molecule that donates a pair of electrons to a metal atom or ion in forming a coordination complex. Ligands
are Lewis bases e.g. H2O, CN-, Cl- and NH3
Monodentate ligand: it can form one co-ordinate bond in one molecule, such as NH3, H2O
Bidentate ligand: it can form two co-ordinate bonds in one molecule, such as ethylenediamine
Polydentate ligand: it can form more than two co-ordinate bonds in one molecule, such as EDTA
It has potential to donate 6 of its electron pair and become EDTA4- and a hexadentate ligand.
Chelate effect
Complexes with polydentate ligand (e.g. EDTA) are most stable and favorable to be formed.
Because polydentate ligands have more binding sites, so it requires fewer moles of polydentate ligands to satisfy the “need” of the metal ions. As
shown in the chemical equation, the reaction is moved from order to disorder (more moles of products than reactants), leading to a highly
positive value of entropy.
According to the equation 𝛥𝛥𝐺𝐺 ⊖ = 𝛥𝛥𝐻𝐻⊖ − 𝑇𝑇𝛥𝛥𝑆𝑆 ⊖ , highly positive entropy will give an highly negative value of Gibb’s free energy, so the
reaction is spontaneous, meaning that the formation of [Cu(EDTA)]2- is favourable.
Complexes
Transition metal ions have relatively high charges and small sizes allowing them to attract ligands’ lone pairs of electrons. The number of dative
bonds from ligands to the central ion is called the coordination number. Ligands can be exchanged.
Complexes: co-ordinate bonds between a metal ions and negative ions or substances with a lone pair.
Metal ion is Lewis acid – electron pair acceptor
Ligand is Lewis base – electron pair donor
Coordination Number
Numbers of co-ordinate bonds around a metal ion in a complexes = coordination number
19
Coordination number = 4: The shape of the complexes is tetrahedral or square planar
Splitting d-orbitals
When ligands approach the metal, in octahedral shape, they move in along the axis, so the orbital on the axis face more repulsion by electric field created by
the incoming ligands. Therefore, they have more energy.
Similarly, orbitals between the axis are influenced less by the electric field created by incoming ligands, Therefore, they have less energy.
20
The d-orbitals are split into two energy levels; the difference between two energy levels is denoted as Δ𝑜𝑜
Colour formation
Colour of the light absorbed by the substance is complementary to the colour observed by us, showing on
the colour wheel. For example, Fe2+ is green in colour, which means it must absorb red colour from the visible
light.
When visible light passes through the substance, one electron will be excited to the higher energy d-orbital.
When it falls back, it gives out energy which falls in the visible light range due to the small gap
between two d-orbital energy levels. This dexcitation will show colour.
The difference between the d-orbital energy levels (Δ𝑜𝑜 ) will affect the energy released by
dexication, thereby showing different colours.
• Diamagnetic: have all electrons paired up, so has no effects under magnetic field.
• Paramagnetic: have unpaired electrons; slightly attracted by a magnetic field and the material does not retain the magnetic properties when
the external field is removed.
• Ferromagnetic: have unpaired electrons; exhibit a strong attraction to magnetic fields and are able to retain their magnetic properties after the
external field has been removed.
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Topic 4: Chemical bonding and structure
4.1 Ionic bonding and structure
U1 Positive ions (cations) form by metals losing valence electrons.
U2 Negative ions (anions) form by non-metals gaining electrons.
U3 The number of electrons lost or gained is determined by the electron configuration of the atom.
U4 The ionic bond is due to electrostatic attraction between oppositely charged ions.
U5 Under normal conditions, ionic compounds are usually solids with lattice structures.
A1 Deduction of the formula and name of an ionic compound from its component ions, including polyatomic ions.
A2 Explanation of the physical properties of ionic compounds (volatility, electrical conductivity and solubility) in terms of their structure.
Ionic bonding
Ionic bonding occurs between elements that have a large difference in electronegativity (typically larger than 1.8). The atom with the low
electronegativity (the metal) loses an electron and becomes a cation. The atom with the high electronegativity (the non-metal) gains the electron
and becomes an anion. As a result there is an electrostatic attraction(not a real bond)between the two ions.
In NaCl, for example, chlorine already has noble gas configuration (it is in the form of diatomic molecules), but the energy given out when the
ionic lattice is formed is sufficient to break the bond in the chlorine molecule to give atoms. Each sodium atom gives an electron to a chlorine
atom. In the lattice each cation is surrounded by 6 anions and vice versa.
Ionic bonding only happens when a electron transferred from a metal to a non-metal
Properties of ionic compounds
• Dissolve in water (ions are free to move, so it conducts electricity)
• Molten ionic compound conducts electricity (ions are free to move)
• In solid state, ionic compound doesn't conduct electricity because ions are not free
• High melting point (in solid state ionic compound has giant lattice structure)
• Electronegativity difference ranges from 4 to 1.8
22
Lewis structures
In Lewis structures, lone pairs of electrons can be depicted by two crosses, two dots or a line. A bond can be shown as a line (or double line for
double bonds).
Polar bonds
When the atoms are different the more electronegative atom exerts a greater attraction for the electron pair, becoming more electron rich
resulting in a polar bond. Bigger difference in electronegativities means a more polar bond. Polar bond ranges from 1.8 – 0.7 electronegativity
difference.
Non-polar
Ionic bonds Polar covalent covalent
4 1.8 0.7 0
• Bond length is a measure of the distance between two nuclei. Bond strength is described in terms of bond enthalpy. Multiples bonds have a
greater number of shared electrons and so have a stronger force of electrostatic attraction between the bonded nuclei. Thus there is a greater
pulling power on the nuclei, bringing them closer together, resulting in bonds that are shorter and stronger than single bonds.
Extended Octet
The exceptions to the octet rule are:
• small atoms like B and Be form stable molecules with fewer than eight electrons (an incomplete octet)
23
• atoms of elements in the third period and below may expand their octet by using d orbitals in their valence shell. This arrangement is
possible because the d orbitals available in the valence shell of these atoms have energy values relatively close to those of the p
orbitals.
• In period 3, after phosphorus, we can see extended octet happening, due to an empty d-orbital where electrons can be excited to.
Resonance
Delocalisation is a characteristic of π bonds where there is more than one possible position for a double bond within a molecule (when there are
resonance structures).
VSEPR theory
VSEPR (valence shell electron pair repulsion) theory states that pairs of electrons arrange themselves so that they are as far apart from each
other as possible.
Each molecule has bond pairs of lone pairs of electron, where they can be found is called electron dense region or charged centres. Charged
centres are indentified only around centre atoms. Depending on how many charged centre, we can figure out the geometry of electron pair
distribution; therefore, we can then find the actual shape of molecules.
Bond pairs have more space to move due to overlap of orbitals so the repulsion between them is relatively low. However, lone pairs have less
space because they are restricted to the certain orbital, so the repulsion between them is larger. Due to this, whenever lone pair presents, it takes
more space so will push bond pairs closer. Therefore, for every one lone pair presents, 2.5°will be reduced from the main angle.
Lone pair electrons don’t account for the shape of the molecules.
24
Number of Geometrical
Number of bonding Number of non-
charge arrangement of Shape and angle Visual aid
pairs bonding pairs
centres charge centres
linear
2 linear 2 0
180°
Linear
2 linear 1 1
180°
Triangular planar
3 Triangular planar 3 0
120°
V-shaped
3 Triangular planar 2 1
117.5°
tetrahedral
4 tetrahedral 4 0
109.5°
Triangular
4 tetrahedral 3 1 pyramidal
107°
v-shaped
4 tetrahedral 2 2
104.5°
Polarity
The prerequisite of polar molecules is polar covalent bonds (electronagetivity difference 1.8-0.7)
Polar bonds will result in a denser region of electron cloud closer to an atom, creating a dipole moments.
If dipole moments cancel out, the molecule is non-polar, if not, this molecule is polar.
26
Number of Geometrical
Number of bonding Number of non-
charge arrangement of Shape and angle Polarity (one type of atom)
pairs bonding pairs
centres charge centres
linear
2 linear 2 0 Non-polar
180°
Linear
2 linear 1 1 Non-polar
180°
Triangular planar
3 Triangular planar 3 0 Non-polar
120°
V-shaped
3 Triangular planar 2 1 polar
117.5°
tetrahedral
4 tetrahedral 4 0 Non-polar
109.5°
Triangular
4 tetrahedral 3 1 pyramidal Polar
107°
V-shaped
4 tetrahedral 2 2 Polar
104.5°
Triangular
5 Triangular bipyramidal 5 0 bipyramidal Non-polar
90°,120°
See saw
5 Triangular bipyramidal 4 1 Polar
117.5°,87.5°
T-shape
5 Triangular bipyramidal 3 2 Polar
90°
Linear
5 Triangular bipyramidal 2 3 Non-polar
180°
Octahedral
6 Octahedral 6 0 Non-polar
90°
Square pyramidal
6 Octahedral 5 1 Polar
87.5°
Square planar
6 Octahedral 4 2 Non-polar
90°
T-shape
6 Octahedral 3 3 Polar
90°
Linear
6 Octahedral 2 4 Non-polar
90°
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4.4 Intermolecular forces
U1 Intermolecular forces include London (dispersion) forces, dipole-dipole forces and hydrogen bonding.
U2 The relative strengths of these interactions are London (dispersion) forces <dipole-dipole forces < hydrogen bonds.
A1 Deduction of the types of intermolecular force present in substances, based on their structure and chemical formula.
A2 Explanation of the physical properties of covalent compounds (volatility, electrical conductivity and solubility) in terms of their structure and intermolecular
forces.
Metallic bonding
In the metal, the valence electrons detached from atoms creating a sea of electrons. A metallic bond is the attraction between positive metal
ions and electron cloud. It can be described as “metal ions surrounded by a cloud of delocalised electrons (a sea of electrons)”
Properties of metals
• Metals are good conductors of heat and electricity because they contain mobile charges (free electrons)
• Metals are malleable and ductile because the layers of cations can slide over each other without breaking more bonds than are made.
• Metals have high melting point and boiling point due to strong forces between positive ions and electrons.
Bonding Properties
Some polar covalent molecules, however, in conditions where they can ionise will conduct electricity. For example, HCl dissolved in water
(hydrochloric acid) is an electrical conductor.
Strength of metallic bonding
• Radius of the ion (larger radius means electrostatic attraction is in larger distance, weaker bonding)
• Charge of the ion (higher the charge, strong the attraction)
Alloys
Mixture of metal, is a kind of metallic solution
Transition metals always form alloys because they have closer atomic radius.
In general, alloys have poor electricity and heat conductivity than pure metal. This is because their size is different, so the flow of electrons is
blocked.
29
Topic 14: Chemical bonding and structure (HL)
14.1 Further aspects of covalent bonding and structure
U1 Covalent bonds result from the overlap of atomic orbitals. A sigma bond (σ) is formed by the direct head-on/end-to-end overlap of atomic orbitals, resulting
in electron density concentrated between the nuclei of the bonding atoms. A pi bond (π) is formed by the sideways overlap of atomic orbitals, resulting in
electron density above and below the plane of the nuclei of the bonding atoms.
U2 Formal charge (FC) can be used to decide which Lewis (electron dot) structure is preferred from several. The FC is the charge an atom would have if all
atoms in the molecule had the same electronegativity. FC = (Number of valence electrons)-½(Number of bonding electrons)-(Number of non-bonding
electrons). The Lewis (electron dot) structure with the atoms having FC values closest to zero is preferred.
U3 Exceptions to the octet rule include some species having incomplete octets and expanded octets.
U4 Delocalization involves electrons that are shared by/between all atoms in a molecule or ion as opposed to being localized between a pair of atoms.
U5 Resonance involves using two or more Lewis (electron dot) structures to represent a particular molecule or ion. A resonance structure is one of two or more
alternative Lewis (electron dot) structures for a molecule or ion that cannot be described fully with one Lewis (electron dot) structure alone.
A1 Prediction whether sigma (σ) or pi (π) bonds are formed from the linear combination of atomic orbitals.
A2 Deduction of the Lewis (electron dot) structures of molecules and ions showing all valence electrons for up to six electron pairs on each atom.
A3 Application of FC to ascertain which Lewis (electron dot) structure is preferred from different Lewis (electron dot) structures.
A4 Deduction using VSEPR theory of the electron domain geometry and molecular geometry with five and six electron domains and associated bond angles.
A5 Explanation of the wavelength of light required to dissociate oxygen and ozone.
A6 Description of the mechanism of the catalysis of ozone depletion when catalysed by CFCs and NOx.
Sigma (σ ) bonds
Sigma bonds result from axial (head-on) overlap of s, p and hybrid orbitals in different combinations.
Pi (π) bonds
Pi bonds result from sideways overlap of parallel orbitals and consist of two regions of electron density (two overlaps). Pi bonds are weaker than
sigma bonds as their electron density is further from the positive charge of the nucleus.
Least formal charge means the most stable atom, suggesting that this kind of structure is correct. If FC is the same, using electro negativity to
deduce, more electronegative atom carries negative formal charge.
As shown in the molecule [OCN]- above, left configuration has largest formal charge, so it cannot be the correct structure. Middle and the right
one have the same formal charge; but oxygen in the right one, as more electronegative atom, has the negative formal charge. So the right one is
the correct structure of [OCN]-
30
VSEPR Theory on 5 and 6 charged centre
90° Triangular
5 0
120° bipyramidal
see saw
87.5°
4 1 (distorted
Triangular 117.5°
5 tetrahedral)
bipryramidal
3 2 90° T-shaped
2 3 180° linear
6 0 90° octahedral
square
5 1 87.5°
pyramidal
6 octahedral
4 2 90° square planar
3 3 90° T-shaped
2 4 180° Linear
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14.2 Hybridisation
U1 A hybrid orbital results from the mixing of different types of atomic orbitals on the same atom.
A1 Explanation of the formation of sp3, sp2 and sp hybrid orbitals in methane, ethene and ethyne.
A2 Identification and explanation of the relationships between Lewis (electron dot)structures, electron domains, molecular geometries and types of hybridization.
Hybridisation
Hybridisation is the process whereby unequal atomic orbitals within an atom mix to form new hybrid atomic orbitals which are the same as each
other, but different from the original orbitals. Hybrid orbitals form stronger bonds by allowing greater overlap. Experimental evidence suggests
that bonds in an molecule have equal length, which support the idea of hybridisation.
sp3 hybridisation
When carbon forms four single bonds (e.g. CH4), it undergoes sp3 hybridisation:
sp2 hybridisation
When carbon forms a double bond (e.g. C2H4), it undergoes sp2 hybridisation:
sp hybridisation
When carbon forms a triple bond (e.g. C2H2), it undergoes sp hybridisation:
32
Hybridisation and molecular shape
The shape of a molecule can be used to determine the type of hybridisation that has occurred:
• tetrahedral arrangement ↔ sp3 hybridised
• planar triangular arrangement ↔ sp2 hybridised
• linear arrangement ↔ sp hybridised
33
Topic 5: Energetics/ thermochemistry
5.1 Measuring energy changes
U1 Heat is a form of energy.
U2 Temperature is a measure of the average kinetic energy of the particles.
U3 Total energy is conserved in chemical reactions.
U4 Chemical reactions that involve transfer of heat between the system and the surroundings are described as endothermic or exothermic.
U5 The enthalpy change (ΔH) for chemical reactions is indicated in kJ mol-1.
U6 ΔH values are usually expressed under standard conditions, given by ΔH°, including standard states.
A1 Calculation of the heat change when the temperature of a pure substance is changed using 𝑞𝑞 = mcΔ𝑇𝑇.
A2 A calorimetry experiment for an enthalpy of reaction should be covered and the results evaluated.
IB definitions
Exothermic reaction – An exothermic reaction is one that releases heat to the surroundings as a result of forming products with
stronger bonds than the reactants. Exothermic reactions have a negative ΔH value.
Endothermic reaction – An endothermic reaction is one that absorbs heat from the surroundings as a result of forming products
with weaker bonds than the reactants. Endothermic reactions have a positive ΔH value.
Standard enthalpy change of reaction –Standard enthalpy change is the heat transferred during a reaction carried out under
standard conditions: Unit: heat per mole (KJmol-1)
• pressure 100 kPa
• temperature 298 K
• all substances pure and in their standard state
Bonding in reaction
• bond making release energy (more stable)
• bond breaking require energy (less stable)
• reaction energy release = bond making – bonding breaking = energy of products –energy of reactants
Measurement of energy
Q = m × c × Δt
Specific heat capacity: amount of energy required to change the temperature of 1kg of substance by 1 degree
34
Enthalpy of formation
Enthalpy change when 1 mole of a molecule is formed from its element in their standard state
1
H2 (g) + O2 (g) → H2 O(l)
2
**Only 1 mole of product should be made**
Enthalpy of combustion
Enthalpy change is released when 1 mole of a substance burns completely with oxygen under standard condition
Enthalpy experiments
Enthalpy calculations
𝑄𝑄 𝑚𝑚𝑚𝑚∆𝑇𝑇
∆𝐻𝐻 = =
𝑛𝑛 𝑛𝑛
Where n is the number of moles reacted (in the combustion experiment this can be calculated from the change in mass of the fuel burner)
Determining temperature change from graphs
You need to extrapolate backwards in order to compensate for the heat loss.
35
Hess’s Law
Total enthalpy change = the sum of all intermediated steps
Problem solving
IB definitions
Bond enthalpy–enthalpy change is required when 1 mole of bonds are broken to form atoms in their gaseous state. For
example, X2(g) → 2X(g)
It is an average value because it takes account of the different energies in a bond between the same atoms in different molecules.
36
Topic 15: Energetics/thermochemistry (HL)
15.1 Energy cycles
U1 Representative equations (eg. M+(g)M+(aq)) can be used for enthalpy/energy of hydration, ionization, atomization, electron affinity, lattice, covalent bond
and solution.
U2 Enthalpy of solution, hydration enthalpy and lattice enthalpy are related in an energy cycle.
A1 Construction of Born-Haber cycles for group 1 and 2 oxides and chlorides.
A2 Construction of energy cycles from hydration, lattice and solution enthalpy. For example dissolution of solid NaOH or NH4Cl in water.
A3 Calculation of enthalpy changes from Born-Haber or dissolution energy cycles.
A4 Relate size and charge of ions to lattice and hydration enthalpies.
A5 Perform lab experiments which could include single replacement reactions in aqueous solutions.
IB definitions
Standard enthalpy of solution–one mole of an ionic solid breaks into its aqueous ions in solution in standard state
Standard enthalpy of hydration –one mole of gaseous ions becomes aqueous ions in standard state
Lattice enthalpy –enthalpy change when one mole of an ionic compound breaks down into its ions in the gaseous state
Enthalpy of atomisation –enthalpy change when one mole of substance change state from solid to gas
Oxides Chlorides
−∆𝐇𝐇𝐟𝐟° + ∆𝐇𝐇𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢
° °
+ 𝐁𝐁𝐁𝐁𝐁𝐁𝐁𝐁 𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄 + 𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈𝐈 𝐞𝐞𝐞𝐞𝐞𝐞𝐞𝐞𝐞𝐞𝐞𝐞 + 𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄 𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚𝐚 = ∆𝐇𝐇𝐥𝐥𝐥𝐥𝐥𝐥𝐥𝐥𝐥𝐥𝐥𝐥𝐥𝐥
Factors affect lattice enthalpy value:
37
• Charge of the ions (greater charge, stronger interaction, greater lattice enthalpy value)
• Distance (smaller size, stronger interaction, greater enthalpy value)
Energy cycle:
Lattice enthalpy: solid to gaseous ions
° ° °
∆Hsolution = ∆Hlattice + ∆Hhydration
The fact that we use standard conditions implies that the temperature is 298K.
38
Calculating ΔG
⊖
∆𝐺𝐺reaction = � ∆𝐺𝐺𝑓𝑓⊖ (products) − � ∆𝐺𝐺𝑓𝑓⊖ (reactants)
Depending on the values of ΔH and ΔS, a reaction might become spontaneous at a certain temperature.
39
Topic 6: Chemical kinetics
6.1 Collision theory and rates of reaction
U1 Species react as a result of collisions of sufficient energy and proper orientation.
U2 The rate of reaction is expressed as the change in concentration of a particular reactant/product per unit time.
U3 Concentration changes in a reaction can be followed indirectly by monitoring changes in mass, volume and colour.
U4 Activation energy (Ea) is the minimum energy that colliding molecules need in order to have successful collisions leading to a reaction.
U5 By decreasing Ea, a catalyst increases the rate of a chemical reaction, without itself being permanently chemically changed.
A1 Description of the kinetic theory in terms of the movement of particles whose average kinetic energy is proportional to temperature in Kelvin.
A2 Analysis of graphical and numerical data from rate experiments.
A3 Explanation of the effects of temperature, pressure/concentration and particle size on rate of reaction.
A4 Construction of Maxwell–Boltzmann energy distribution curves to account for the probability of successful collisions and factors affecting these, including the
effect of a catalyst.
A5 Investigation of rates of reaction experimentally and evaluation of the results.
A6 Sketching and explanation of energy profiles with and without catalysts.
Collision theory
According to collision theory, for a reaction to occur three criteria must be met:
• the particles must collide
• they must collide with the appropriate geometry or orientation so that the reactive parts of the particles come into contact
• they must collide with sufficient energy (the activation energy)
particle size The greater the particle size, the smaller the exposed surface area. Reduced frequency
decreases rate
(surface area) of successful collision. So the rate of reaction decreases
Catalyst will decrease the activation energy, providing an alternative route for the
catalysts increases rate reaction. More particles will have energy beyond the activation energy. So the frequency
of successful collision will increase.
Catalyst:
• Catalyst is able to decrease the activation energy
• Heterogeneous catalyst: different state between catalyst and reactants
• Homogeneous catalyst: same state between catalyst and reactants
40
• Increasing the temperature lowers the peak of the curve and moves it to the right, more particles have enough energy to react
• Adding a catalyst reduces the activation energy, more particles have enough energy to react
Rate expression
𝐴𝐴 + 𝐵𝐵 → products
The rate constant (k) is the constant of proportionality in the rate expression. It has a specific value for a specific reaction at a specific
temperature. The units vary depending on the expressions.
The overall order of the reaction is m + n
The order with respect to a reactant is the power it is raised to in the rate expression.
Rate constant is only affected by temperature.
Rate expression is only focused on reactants.
41
Units of rate constant
2
Rate = k[A]3 or
Rate = k[A] or
Rate = k Rate = k[A] Rate = k[A][B]2 or
Rate = k[A][B]
Rate = k[A][B][C]
dA
− =k
dt
dA = −k × dt
Af t
� dA = − � k dt
A0 0
Af − A0 = −k × t
Af = A0 − kt
1
× dA = −k × dt
A
Af t
1
� dA = − � k dt
A0 A 0
Af
In � � = −kt
A0
Af = Ao × e−kt
42
• In first order reaction: Final concentration (Af) = Initial concentration (A0) ×e-kt
1
× dA = −k × dt
A2
Af t
1
� dA = − � k dt
A0 A2 0
𝟏𝟏 𝟏𝟏
− + = −𝒌𝒌𝒌𝒌
𝐀𝐀𝐟𝐟 𝑨𝑨𝟎𝟎
𝟏𝟏 𝟏𝟏
= + 𝒌𝒌𝒌𝒌
𝐀𝐀𝐟𝐟 𝑨𝑨𝟎𝟎
𝟏𝟏 𝟏𝟏
• In second order reaction: = + 𝐤𝐤𝐤𝐤
𝐟𝐟𝐟𝐟𝐟𝐟𝐟𝐟𝐟𝐟 𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜 (𝐀𝐀𝐟𝐟 ) 𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢𝐢 𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜𝐜 (𝐀𝐀𝟎𝟎 )
Combined graph
43
Half life: amount of time required for the final concentration to become half of the original amount
Zero order reaction:
1
Af = A0
2
1
A = A0 − kt
2 0
1
kt = A
2 0
𝐀𝐀𝟎𝟎
𝐭𝐭 𝟏𝟏 =
𝟐𝟐 𝟐𝟐𝟐𝟐
2 = 1 + kt × A0
𝟏𝟏
𝐭𝐭 𝟏𝟏 =
𝟐𝟐 𝐤𝐤 × 𝐀𝐀𝟎𝟎
The concentration vs. time graphs for first and second orders look quite similar however, first order reactions have a constant half-life, whereas
with second order reactions each half-life is twice the preceding one.
44
Reaction mechanism
Most reactions that occur at a measurable rate occur as a series of simple steps. The sequence of steps is known as the reaction mechanism.
The individual steps (elementary steps) usually cannot be observed directly. Intermediates are substances that are made in one step and used
up in another. The sum of the elementary steps should cancel to give the original equation. The term molecularity is used in reference to an
elementary step to indicate the number of reactant species involved. If a reaction has three, four or more species combining, it is likely that it can
be split into steps.
The rate-determining step
The rate equation can be known by knowing the reaction mechanism, specifically the slowest step, which acts as a limit on the rate and is
therefore called the rate-determining step.
The rate equation is also equal to the rate constant (k) multiplied by the concentrations of the substances raised to the power of their respective
coefficients in the rate-determining step.
The order of reaction is the exact numbers of molecules involves in the rate determining step.
aA + bB → products (slowstep)
45
Problem solving
If a species is both on the reactant and product side of the overall equation, it is probably a catalyst.
The rate of reaction increases with temperature (we know this already because of collision theory). A common relationship is that 10°C increase
doubles the rate. Looking back at the Maxwell-Boltzmann distribution curve, an increase in temperature means that more particles have an
energy greater or equal to the activation energy. This means that the value of the activation energy will determine temperature’s effect. When the
Ea is larger a temperature rise will make a larger difference, and when the Ea is smaller the temperature change will have a less significant effect.
46
Topic 7: Equilibrium
7.1 Equilibrium
U1 A state of equilibrium is reached in a closed system when the rates of the forward and reverse reactions are equal.
U2 The equilibrium law describes how the equilibrium constant (Kc) can be determined for a particular chemical reaction.
U3 The magnitude of the equilibrium constant indicates the extent of a reaction at equilibrium and is temperature dependent.
U4 The reaction quotient (Q) measures the relative amount of products and reactants present during a reaction at a particular point in time. Q is the equilibrium
expression with non-equilibrium concentrations. The position of the equilibrium changes with changes in concentration, pressure, and temperature
U5 A catalyst has no effect on the position of equilibrium or the equilibrium constant.
A1 The characteristics of chemical and physical systems in a state of equilibrium.
A2 Deduction of the equilibrium constant expression (Kc) from an equation for a homogeneous reaction.
A3 Determination of the relationship between different equilibrium constants (Kc) for the same reaction at the same temperature.
A4 Application of Le Châtelier’s principle to predict the qualitative effects of changes of temperature, pressure and concentration on the position of equilibrium
and on the value of the equilibrium constant.
The reaction has stopped but both forward and backward reactions are still
1 Equilibrium is dynamic occurring at the same rate.
The speed of forward reaction is equal to the speed of backward reaction.
5 Equilibrium can be reached from either direction The reaction can be started with all reactants, all products or a mixture.
Equilibrium constant
Given a reversible reaction,
aA + bB ⇌ cC + dD
The equilibrium expression is the concentration of the products raised to the coefficients in the balanced equation over those of the reactants:
[𝐶𝐶]𝑐𝑐 [𝐷𝐷]𝑑𝑑
𝐾𝐾𝐶𝐶 =
[𝐴𝐴]𝑎𝑎 [𝐵𝐵]𝑏𝑏
A rule of thumb is:
𝐾𝐾𝐶𝐶 > 1 → reaction is towards products
Special cases :
1. In aqueous reaction, if water takes part in, ignore water concentration in Kc expression.
Cu(OH)2 (aq) + 2HCl(aq) ⇌ CuCl2 (aq) + H2 O(l)
[Cu Cl 2 ]
Kc expression (ignore water): 𝐾𝐾𝐶𝐶 = [𝐶𝐶𝐶𝐶 (𝑂𝑂𝑂𝑂)2 ][𝐻𝐻𝐻𝐻𝐻𝐻]2
2. Solid doesn’t show up in Kc expression
47
Le Chatelier’s principle
If any change is imposed on a system that is in equilibrium then the system tends to adjust to a new equilibrium counteracting the change.
• In an exothermic reaction heat can be considered a product, so increasing the temperature will shift the equilibrium towards the
reactants, and decreasing the temperature will shift it to the products
• In an endothermic reaction heat can be considered a reactant
• Increasing pressure shifts the equilibrium to the side with fewer moles of gas, so as to decrease the pressure
• Decreasing pressure shifts it to the side with more moles of gas
• Increasing concentration shifts it to the side with fewer moles of solute
• Decreasing concentration shifts it to the side with more
• A catalyst speeds up the reaction but does not affect the value of the equilibrium constant
Only temperature affects the value of the equilibrium constant
Catalyst has no effect on equilibrium position
The Haber process
The Haber process is the process used to produce ammonia, NH3
N2 (g) + 3H2 (g) ⇌ 2NH3 (g) ∆𝐻𝐻 = −93kJ mol−1
Conditions:
catalyst iron -
Reaction quotient
Kc can only be calculated in equilibrium, while Qc can be calculated at any time in the reaction.
[𝐶𝐶]𝑐𝑐 [𝐷𝐷]𝑑𝑑
𝑄𝑄𝐶𝐶 = [𝐴𝐴]𝑎𝑎 [𝐵𝐵]𝑏𝑏
for aA + bB ⇌ cC + dD
𝑄𝑄𝐶𝐶 >𝐾𝐾𝐶𝐶 → more products, less reactants, equilibrium will shift towards reactants till Qc = Kc
𝑄𝑄𝐶𝐶 <𝐾𝐾𝐶𝐶 →more reactants, less products, equilibrium will shift towards products till Qc = Kc
48
Topic 17: Equilibrium (HL)
17.1 The equilibrium law
U1 Le Châtelier’s principle for changes in concentration can be explained by the equilibrium law.
U2 The position of equilibrium corresponds to a maximum value of entropy and a minimum in the value of the Gibbs free energy.
U3 The Gibbs free energy change of a reaction and the equilibrium constant can both be used to measure the position of an equilibrium reaction and are related
by the equation∆G = −RT Ink
A1 Solution of homogeneous equilibrium problems using the expression for Kc.
A2 Relationship between ΔG and the equilibrium constant.
A3 Calculations using the equation.∆G = −RT Ink
Problem solving
Calculating the equilibrium concentrations given KC and initial conditions
The equilibrium constant KC for the reaction
SO3 (g) + NO(g) ⇌ NO2 (g) + SO2 (g)
was found to be 6.78 at a specified temperature. If the initial concentrations of NO and SO3 were both 0.03 mol dm-3, what would
be the equilibrium concentration of each component?
Solution
SO3(g) + NO(g) ⇌ NO2(g) + SO2(g)
Change -x -x x x
[NO2 ][SO2 ] 𝑥𝑥 2
𝐾𝐾𝐶𝐶 = = = 6.78
[SO3 ][NO] (0.03 − 𝑥𝑥)2
[reactant]initial ≈ [reactant]equilibrium
The thermal decomposition of water has a very small value of KC. At 1000°C, KC = 7.3 × 10-18 for the reaction
A reaction is set up at this temperature with an initial H2O concentration of 0.10 mol dm-3. Calculate the H2 concentration at
equilibrium.
49
Solution
2H2O(g) = 2H2(g) + O2(g)
Equilibrium 0.10 - 2x 2x x
Kc Changes
Effect on equilibrium expression Effect on KC
°
𝐾𝐾𝐶𝐶 < 1 → reaction is towards reactants, so the forward reaction is NOT spontaneous: ∆Gforward reaction >0
°
𝐾𝐾𝐶𝐶 >1→∆Gforward reaction =0
In Kc
1
T
∆G°
Gradient = −
R
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Topic 8: Acids and bases
8.1 Theories of acids and bases
U1 A Brønsted–Lowry acid is a proton/H+ donor and a Brønsted–Lowry base is a proton/H+ acceptor.
U2 Amphiprotic species can act as both Brønsted–Lowry acids and bases.
U3 A pair of species differing by a single proton is called a conjugate acid-base pair
A1 Deduction of the Brønsted–Lowry acid and base in a chemical reaction.
A2 Deduction of the conjugate acid or conjugate base in a chemical reaction.
IB definitions
• pH below 7
• react with hydroxides to form a salt and water • pH above 7
• react with metal oxides to form a salt and water • alkalis are bases that dissolve in water
• react with ammonia to form a salt • turns litmus blue
• react with metals to form a salt and hydrogen gas • is prepared by metal oxide and water
• react with carbonates forming a salt, water and carbon
dioxide
• turns litmus pink
Monoprotic acid: one H+ can be given away per molecule (HCl, CH3COOH)
Diprotic acid: two H+ can be given away per molecule (H2SO4)
Triprotic acid: three H+ can be given away per molecule (H3PO4)
Neutralisation:
• Salt and water are produced in neutralisation
• Neutralisation reaction is always exothermic, the enthalpy of neutralisation is always negative.
Amphoteric substances can react with acids and bases such as Al2O3
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8.3 The pH scale
U1 pH = -log[H+(aq)] and [H+] = 10-pH.
U2 A change of one pH unit represents a 10-fold change in the hydrogen ion concentration [H+].
U3 pH values distinguish between acidic, neutral and alkaline solutions.
U4 The ionic product constant, Kw = [H+][OH−] = 10-14 at 298 K.
Acids have a pH below 7. Neutral substances have a pH of exactly 7. Bases have a pH greater than 7. The greater the pH the more alkaline a
substance and the lower the pH the more acidic it is.
pH = − log[H +]
This means that decreasing one pH unit represents a ten-fold increase in hydrogen ion concentration and increasing one unit represents a ten-
fold increase. A two unit change represents a one hundred-fold change and so on.
Ionic product of water
H2 O + H2 O ⇌ H3 O+ + OH −
K c = [H3 O+ ][OH −]
In this case, Kc is equal to Kw, which is the ionic product of water, measuring the natural disassociation degree of water. Kw = 10-14
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Distinguish between strong and weak acid
Using universal pH paper or pH sensor: the one with lower pH is the stronger acid and the one with higher pH is the stronger base. (same concentration
Acid-base titration: faster rate of titration leads to stronger acid/base, lower rate of titration leads to a weaker acid/base. However, the volume required is
the same between the weak and strong acid. The weak acid will also disassociate completely since the equilibrium will shift to the product side due to
decreasing amount of H+
Conductivity of solutions: stronger the acid/base, it will have high conductivity due to the presence of more ions.
Rate of reaction will metal oxides, metals and carbonates.
Rain is always acidic because carbon dioxide from the atmosphere dissolves in rain water and gives natural pH of 5.6
When the rain water has a pH below 5.6, it is considered as acid rain. Sources of the acid rain include: HNO3, HNO2, H2SO4 and H2SO3
H2 O + SO2 → H2 SO3
H2 O + SO3 → H2 SO4
H2 O + NO2 → HNO3 + HNO2
HNO2 + O2 → HNO3
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Topic 18: Acids and bases (HL)
18.1 Lewis acids and bases
U1 A Lewis acid is a lone pair acceptor and a Lewis base is a lone pair donor.
U2 When a Lewis base reacts with a Lewis acid a coordinate bond is formed.
U3 A nucleophile is a Lewis base and an electrophile is a Lewis acid.
A1 Application of Lewis’ acid–base theory to inorganic and organic chemistry to identify the role of the reacting species.
Lewis theory
IB definitions
Lewis base: molecules usually have a lone pair of electron to give. e.g. ammonia and water
Lewis acid: molecules usually don’t have a complete octet e.g. BF3, AlCl3, BeCl2
Coordinate bonds will be formed between a Lewis acid and a Lewis base.
Lewis acid (incomplete octet): they are electrophiles (electron loving, accepting electron pairs)
Lewis base (lone pair of electrons): they are nucleophiles (electron hating, donating electrons)
pH and pOH
pH = − log[H +]
pOH = − log[OH − ]
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pH + pOH = p𝐾𝐾𝑊𝑊 (= 14 at 25°C)
Weak acids
A weak acid dissociates partially in water:
Weak bases
Weak bases also dissociate partially. This can be expressed as:
Since weak acids and bases only dissociate slightly they have low Ka or Kb respectively (remember that if the equilibrium lies to the left, Kc<< 1).
Since strong acids and bases dissociate fully, they will have larger Ka or Kb respectively (remember if equilibrium lies to right, Kc>> 1).
18.3 pH curves
U1 The characteristics of the pH curves produced by the different combinations of strong and weak acids and bases.
U2 An acid–base indicator is a weak acid or a weak base where the components of the conjugate acid–base pair have different colours.
U3 The relationship between the pH range of an acid–base indicator, which is a weak acid, and its pKa value.
U4 The buffer region on the pH curve represents the region where small additions of acid or base result in little or no change in pH.
U5 The composition and action of a buffer solution.
A1 The general shapes of graphs of pH against volume for titrations involving strong and weak acids and bases with an explanation of their important features.
A2 Selection of an appropriate indicator for a titration, given the equivalence point of the titration and the end point of the indicator.
A3 While the nature of the acid–base buffer always remains the same, buffer solutions can be prepared by either mixing a weak acid/base with a solution of a
salt containing its conjugate, or by partial neutralization of a weak acid/base with a strong acid/base.
A4 Prediction of the relative pH of aqueous salt solutions formed by the different combinations of strong and weak acid and base.
A buffer solution is resistant to changes in pH on the addition of small amounts of strong acid or alkali. They are a mixture of two solutions such
that it contains the two species of a conjugate acid-base pair. Acidic buffers maintain the pH below 7 and basic buffers maintain it above 7.
Composition of the buffer solution
• Acidic buffer is made by a weak acid and the salt of this weak acid (same concentration and volume) e.g. CH3COOH and CH3COONa
• Basic buffer is made by a weak base and the salt of this weak base (same concentration and volume) e.g. NH4OH and NH4NO3
• Because the weak acid/base disassociates partially in water, it will create equilibrium with the reactant side being the acid/base and
product side being the ion of acid/base.
• When adding H+/OH-, large concentration of both sides (products/reactants) will resist the shift of the equilibrium, thereby stabilising the
pH value.
• For example, when mixing the same concentration and volume of CH3COOH and CH3COONa together, we can the equilibrium like this:
CH3COOH⇌ CH3COO- + H+
The concentration of both CH3COOH and CH3COO- is both high, it resists the shift of equilibrium.
Step 3: Write the equilibrium expression and rearrange depending on what you want to find:
[salt] [salt]
pH = p𝐾𝐾𝑎𝑎 + log & pOH = p𝐾𝐾𝑏𝑏 + log
[acid] [base]
Acid-base titration
Strong acid + Strong base Weak acid + Strong base
e.g. HCl + NaOH e.g. CH3COOH + NaOH
• The leftmost and rightmost points represent the pH of the acid and base respectively
• the big vertical jump is the point of inflection
• the equivalence point is where the solutions neutralise
• pH = pKa or pOH = pKb at the half-equivalence point, where a buffer is created
• when a weak acid is added to a weak base, it is difficult to determine the equivalence point. Instead other techniques are used.
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Indicators
Indicators are weak acids or weak bases in which the undissociated and dissociated forms have different colours.
HIn(aq) ⇌ H + (aq) + In− (aq)
colour A colour B
Le Chatelier’s principle
Increasing the H+ concentration moves the equilibrium to the left
Increasing the OH- concentration moves the equilibrium to the right
Colour change
Indicators change colour when the pH is equal to their pKa, at the midpoint in the equilibrium, so that [HIn] = [In-]
[H+ ][In−] [H +][In−]
𝐾𝐾𝑎𝑎 = = → p𝐾𝐾𝑎𝑎 = pH
[HIn] [HIn]
This is known as the change point or the end point of the indicator. At this point, the addition of a very small volume of acid or base will shift the
equilibrium as described above, and so cause the indicator to change colour.
Choosing the appropriate indicator
An indicator will be effective in signalling the equivalence point of a titration when its end point coincides with the pH at the equivalence point.
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Topic 9: Redox processes
9.1 Oxidation and reduction
U1 Oxidation and reduction can be considered in terms of oxygen gain/hydrogen loss, electron transfer or change in oxidation number.
U2 An oxidizing agent is reduced and a reducing agent is oxidized.
U3 Variable oxidation numbers exist for transition metals and for most main-group non-metals.
U4 The activity series ranks metals according to the ease with which they undergo oxidation.
U5 The Winkler Method can be used to measure biochemical oxygen demand (BOD), used as a measure of the degree of pollution in a water sample.
A1 Deduction of the oxidation states of an atom in an ion or a compound.
A2 Deduction of the name of a transition metal compound from a given formula, applying oxidation numbers represented by Roman numerals.
A3 Identification of the species oxidized and reduced and the oxidizing and reducing agents, in redox reactions.
A4 Deduction of redox reactions using half-equations in acidic or neutral solutions.
A5 Deduction of the feasibility of a redox reaction from the activity series or reaction data.
A6 Solution of a range of redox titration problems.
A7 Application of the Winkler Method to calculate BOD.
IB definitions
Oxidation – the loss of an electron, the gain of oxygen, the loss of hydrogen or the increase in oxidation number
Reduction – the gain of an electron, the loss of oxygen, the gain of hydrogen or the decrease in oxidation number
OIL RIG: Oxidation is gain, Reduction is loss
2. For group one and group two ions: oxidation number = charges (+1/+2)
5. Group 17 ions has an oxidation number of -1 when forming a compound with metal ions.
IB definitions
Oxidising agent – a substance that readily oxidizes other substances. Oxidizing agents are thus reduced
Reducing agent – a substance that readily reduces other substances. Reducing agents are thus oxidized.
More reactive metals are stronger reducing agents than less reactive metals. A more reactive metal is able to reduce the ions of a less reactive
metal. More reactive non-metals are stronger oxidising agents than less reactive non-metals. A more reactive non-metal is able to oxidise the
ions of a less reactive non-metal.
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Writing half-equations (in H+ medium)
1. Separating reduction and oxidation side of the reaction
2. Balance the atoms other than H and O
3. Balance each half-equation for O by adding H2O as needed.
4. Balance each half-equation for H by adding H+ as needed.
5. Balance each half-equation for charge by adding electrons to the sides with the more positive charge.
Writing the redox equation
6. Equalize the number of electrons in the two-half equations by multiplying each appropriately.
Add the two half-equations together, cancelling out anything that is the same on both sides, which includes electrons.
Problem solving
6. Combine two half equations together by multiplying the equations to cancel the electrons
Winkler method
1. Fix oxygen: 2Mn2+ + 𝐎𝐎𝟐𝟐 + 4OH− → 2MnO(OH)2
Fix all oxygen in the water to MnO(OH)2 the solution colour changes from colourless to brown
2. Convert to iodine: MnO(OH)2 + 2I− + 4H+ → 𝐈𝐈𝟐𝟐 + Mn2+ + 3H2 O
The solution colour changes from brown to gold (fully dissolved); add starch into the solution as indication, the solution turns dark blue
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3. Titration: I2 + 2S2 O3 2− → 2I− + S4 O6 2−
In summary: 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏 O2 in the sample → 2mol MnO(OH)2 → 2mol I2 → 2mol S4 O6 2− → 𝟒𝟒𝟒𝟒𝟒𝟒𝟒𝟒 S2 O3 2− added
C CO2 CH4
N NO3- NH3
S SO42- H2S
P PO43- PH3
1. Air bubbles through the water sample and measure the dissolved oxygen (DO1) using Winkler method
2. Container is sealed with bacteria in the dark for 5 days
3. Measure the dissolved oxygen (DO2) in the sample using Winkler method
4. Calculate BOD = DO1 – DO2
Galvanic cell
If zinc is placed in a copper (II) sulphate solution, electrons are transferred spontaneously from the zinc to copper and energy is released as heat.
Instead of being lost as heat, the energy can be available as electrical energy by separating the two half-reactions into half-cells and allowing the
electrons to flow through a circuit. This is known as an electrochemical, galvanic or voltaic cell.
Half cells generate electrode potentials: when a metal is placed in a solution containing its ions, an equilibrium forms between the oxidised and
normal forms. As atoms become ions they leave their electrons behind them creating a charge separation or electrode potential, the size of which
is determined by the position of the equilibrium. In general, the more reactive a metal, the more negative its electrode potential in its half-cell.
Half-cells connected by a wire are called electrodes. Oxidation always occurs at the anode; reduction always occurs at the cathode. In the
voltaic cell, the anode has a negative charge and the cathode has a positive charge. Electrons flow from the anode to cathode. A salt bridge is a
glass tube that contains an aqueous solution of ions that enables negative charge to be carried in the opposite direction to that of the electrons
(from cathode to anode). This ion movement neutralises any build up of charge and maintains the potential difference.
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Functions of the salt bridge
1. Complete the circuit
2. Physically separates the solutions
3. Reduce liquid junction potential (creates when two solution with different conductivity meetes)
4. Produce ions to neutralise the solution
Notation
The notation used for describing electrochemical cells is:
Electrolytic cell
An electrolytic cell uses an external source of voltage to bring about a redox reaction that would otherwise be non-spontaneous. The reactant
is known as the electrolyte – a molten liquid or aqueous solution of an ionic compound. As the electric current passes through it, redox reactions
occur at the electrodes, removing the charges of the ions or ‘discharging’ them. Oxidation occurs at the positive electrode (anode) –
anions lose electrons - and reduction occurs at the negative electrode (cathode) – positive ions gain electrons.
The current is not passed through the electrolyte by electrons but by the ions as they are mobile.
When the electrolyte is a molten solution, for example NaCl, anions will appear in anode (Na solid) and cations will appear in cathode (Cl2 gas)
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Topic 19: Redox processes (HL)
19.1 Electrochemical cells
U1 A voltaic cell generates an electromotive force (EMF) resulting in the movement of electrons from the anode (negative electrode) to the cathode (positive electrode) via the
external circuit. The EMF is termed the cell potential (Eº).
U2 The standard hydrogen electrode (SHE) consists of an inert platinum electrode in contact with 1 mol dm-3 hydrogen ion and hydrogen gas at 100 kPa and 298 K. The standard
electrode potential (Eº) is the potential (voltage) of the reduction half-equation under standard conditions measured relative to the SHE. Solute concentration is 1 mol dm-3 or
100 kPa for gases. Eº of the SHE is 0 V.
U3 When aqueous solutions are electrolysed, water can be oxidized to oxygen at the anode and reduced to hydrogen at the cathode.
U4 Gº = - nFEº. When Eº is positive, Gº is negative indicative of a spontaneous process. When Eº is negative, Gº is positive indicative of a non-spontaneous process. When Eº is
0, then Gº is 0.
U5 Current, duration of electrolysis and charge on the ion affect the amount of product formed at the electrodes during electrolysis.
U6 Electroplating involves the electrolytic coating of an object with a metallic thin layer.
A1 Calculation of cell potentials using standard electrode potentials.
A2 Prediction of whether a reaction is spontaneous or not using Eo values.
A3 Determination of standard free-energy changes (ΔGo) using standard electrode potentials.
A4 Explanation of the products formed during the electrolysis of aqueous solutions.
A5 Perform lab experiments that could include single replacement reactions in aqueous solutions.
A6 Determination of the relative amounts of products formed during electrolytic processes.
A7 Explanation of the process of electroplating.
• 1M H+ ions
• H2 gas bubbles through the platinum electrode at 100kPa
• At 298K
• the electrode is coated in very fine platinum
• the large surface area makes the reaction happen readily
• platinum is also fairly inert and can also catalyse the dissociation of H2
• Act as a cathode (reduction): 2H+ + 2e− → H2
• Act as an anode (oxidation): H2 → 2H + + 2e−
• SHE always connect to the negative terminal of the voltmeter
Standard electrode potential
When the standard hydrogen electrode is connected to another standard half-cell by an external circuit with a high resistance voltmeter and a salt
bridge, the emf generated is known as the standard electrode potential of the half-cell.
𝐸𝐸 ⊖ cell = 𝐸𝐸 ⊖ half −cell where reduction occurs − 𝐸𝐸 ⊖ half −cell where oxidation occurs = 𝐸𝐸 ⊖ 𝑐𝑐𝑐𝑐𝑐𝑐 ℎ𝑜𝑜𝑜𝑜𝑜𝑜 − 𝐸𝐸 ⊖ 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
The values inserted into this equation must be reduction potentials. The stoichiometry of the equation does not matter.
Gº = - nFEº. When Eº is positive, Gº is negative indicative of a spontaneous process. When Eº is negative, Gº is positive indicative of a non-
spontaneous process. When Eº is 0, then Gº is 0.
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If 𝐸𝐸 ⊖ cell is positive, the reaction is spontaneous as written; if 𝐸𝐸 ⊖ cell is negative, the reaction is non-spontaneous and in fact the reverse reaction
is spontaneous.
Electrolytic cell
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Electroplating
Electroplating is the process of using electrolysis to deposit a layer of a metal on top of another
metal or other conductive substance. An electrolytic cell used for electroplating has the following
features:
• an electrolyte containing the metal ions to be deposited
• the object to be plated as the cathode
• sometimes the anode is made of the same metal which is to be coated because it may be
oxidised to replenish the supply the ions in the electrolyte
Electroplating can be used for various purposes:
• decorative purposes
• corrosion control e.g. zinc is deposited on iron or steel in a process called galvanisation.
This is called sacrificial protection.
• improvement of function e.g. electroplating of chromium on steel improves the wear on steel parts such as hand tools or crankshafts
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Topic 10: Organic chemistry
10.1 Fundamentals of organic chemistry
U1 A homologous series is a series of compounds of the same family, with the same general formula, which differ from each other by a common structural unit.
U2 Structural formulas can be represented in full and condensed format.
U3 Structural isomers are compounds with the same molecular formula but different arrangements of atoms.
U4 Functional groups are the reactive parts of molecules.
U5 Saturated compounds contain single bonds only and unsaturated compounds contain double or triple bonds.
U6 Benzene is an aromatic, unsaturated hydrocarbon.
A1 Explanation of the trends in boiling points of members of a homologous series.
A2 Distinction between empirical, molecular and structural formulas.
A3 Identification of different classes: alkanes, alkenes, alkynes, halogenoalkanes, alcohols, ethers, aldehydes, ketones, esters, carboxylic acids, amines,
amides, nitriles and arenes.
A4 Identification of typical functional groups in molecules eg phenyl, hydroxyl, carbonyl, carboxyl, carboxamide, aldehyde, ester, ether, amine, nitrile, alkyl,
alkenyl and alkynyl.
A5 Construction of 3-D models (real or virtual) of organic molecules.
A6 Application of IUPAC rules in the nomenclature of straight-chain and branchedchain isomers.
A7 Identification of primary, secondary and tertiary carbon atoms in halogenoalkanes and alcohols and primary, secondary and tertiary nitrogen atoms in amines.
A8 Discussion of the structure of benzene using physical and chemical evidence.
Homologous series
The main features of a homologous series are:
1. Successive members of a homologous series differ by one CH2 group
2. All members of a homologous series can be expressed by the same general formula
3. Successive members show a gradation in physical properties
4. The different members have similar chemical properties
The boiling points increase as the chain gets longer as the Van der Waals forces get stronger.
Formulas
The empirical formula shows the simplest ratio of atoms in a compound.
The molecular formula shows the actual number of atoms in a compound.
The structural formula is a representation of a molecule showing how the atoms are bonded together.
Condensed structural
Full structural formula Skeletal formula
formula
H O
∣ ∥
H− C −C−O−H CH3COOH
∣ ∥
H O
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Structural isomers
Structural isomers are compounds with the same molecular formula but with different arrangements of atoms, for example the isomers of hexane
are:
hexane 2-methylpentane 3-methylpentane
2,2-dimethylbutane 2,3-dimethylbutane
• Less branched isomer will have more surface area. So they are more likely to be polarised (induced dipole moment), leading to a higher
boiling point.
• More branched isomer will have less surface area, leading to a lower boiling point.
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Ketone (carbonyl
-oyl- -one*
group)
*fluoro-, chloro,
Halogen C−X
bromo-, iodo-
Phenyl group
*phenyl-
(arenes)
Volatility
We can summarise the effect on volatility of the different functional groups as follows.
most volatile least volatile
alkane > halogenoalkane > aldehyde > ketone > alcohol > carboxylic acid
van der Waals’ → dipole-dipole → hydrogen bonding
increasing strength of molecular attraction →
increasing boiling point
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Solubility
Molecules with functional groups that enable hydrogen bonds to form with water include the alcohols, the carboxylic acids and the amines. So the
smaller members of these series are readily soluble in water. Aldehydes, ketones, amides and esters are less soluble, while halogenoalkanes,
alkanes and alkenes are insoluble.
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1. Initiation
The homolytic fission of the chlorine molecule:
UV light
Cl2 �⎯⎯⎯⎯� Cl ∙ +Cl ∙
2. Propagation
For example:
Cl ∙ +CH4 → CH3 ⋅ +HCl
CH3 ∙ +Cl2 → CH3 Cl + Cl ∙
These reactions are called propagation because they both use and produce free radicals.
3. Termination
Cl ∙ +Cl ∙ → Cl2
CH3 ∙ +Cl ∙ → CH3 Cl
CH3 ∙ +CH3 ∙ → C2 H6
This is when all the radicals are used up in the reaction. Reaction stops.
With hydrogen
Hydrogenation occurs in the presence of a nickel/Platinum catalyst at 150°C e.g.
H H H H H H
Ni catalyst
∣ ∣ ∣ 150°C
∣ ∣ ∣
H − C − C = C − H + H2 �⎯⎯⎯⎯⎯⎯� H − C − C − C − H
∣ ∣ ∣ ∣ ∣ ∣
H H H H H H
propene + hydrogen→propane
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With halogens
Dihalogeno compounds are produced in the reactions between halogens and alkenes. These reactions happen quickly at room temperature
accompanied by the loss of colour of the halogen. There are called halo-ination (e.g. bromination)
H H H H H H
∣ ∣ ∣ fffffffff ∣ ∣ ∣
H − C − C = C − H + Br2 �⎯⎯⎯� H − C − C − C − H
∣ ∣ ∣ ∣ ∣ ∣
H H H H Br Br
propene + bromine → 1,2-dibromopropane
With hydrogen halides
The hydrogen halide (HX) with the weaker bond reacts faster. This means the reaction rate increases down the group. This takes place rapidly at
room temperature e.g.
H H H H H H
∣ ∣ ∣ fffffffff ∣ ∣ ∣
H − C = C − C − H + HCl �⎯⎯⎯� H − C − C − C − H
∣ ∣ ∣ ∣ ∣ ∣
H H H H Cl H
The halide bonds to the carbon with fewer hydrogens bonded to it.
With water
Hydration is the reaction that converts an alkene into an alcohol. Conditions: heat with steam and catalyst of concentrated sulphuric acid.(H+)
Polymerisation
Alkenes (the monomers) can join together to produce long chains called polymers by addition under high pressure.
The hydration of ethene is of industrial significance because ethanol is a very important solvent and so is manufactured on a large scale. The
hydrogenation reaction is used in the margarine industry to saturate oil compounds, making the liquid solid. Polymers can be made into plastic
for bags, water pipes, ropes and so on.
Combustion of Alcohol
When alcohols undergo complete combustion (when oxygen is plentiful), the products are water and carbon dioxide:
2CH3 OH(l) + 3O2 (g) → 2CO2 (g) + 4H2 O(g)
The longer the chain the greater the ∆H
When oxygen is less plentiful, the combustion will produce water and carbon or carbon monoxide.
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2CH3 OH(l) + O2 (g) → 2C(s) + 4H2 O(g)
Oxidation of Alcohols
Combustion involves the complete oxidation of the alcohol molecules, but it is also possible for them to react with oxidising agents which
selectively oxidise the carbon atom attached to the OH group, keeping the carbon skeleton intact, so that useful compounds can be made. In the
lab, acidified potassium dichromate(VI)/potassium manganese(VII) is used as the oxidising agent. Owing to the Cr(VI), this solution is bright
orange. When the mixture is heated, the colour changes to green as the Cr(VI) is reduced to Cr(III). The oxidising agent is usually represented
by [O].
Primary alcohols
Primary alcohols are oxidised in a two-step reaction, first forming the aldehyde and then the carboxylic acid:
H H H O H O
∣ ∣ +[O], heat ∣ ∥ +[O], heat ∣ ∥
H − C − C − OH �⎯⎯⎯⎯⎯⎯� H − C − C − H �⎯⎯⎯⎯⎯⎯� H − C − C − OH
∣ ∣ ∣ ∥ reflux ∣ ∥
H H H O H O
Secondary alcohols
Secondary alcohols are oxidised to the ketone:
H H H H H H
∣ ∣ ∣ +[O], heat ∣ ∣ ∣
H − C − C − C − H �⎯⎯⎯⎯⎯⎯� H − C − C − C − H
∣ ∣ ∣ reflux ∣ ∥ ∣
H OH H H O H
propan-2-ol → propanone
Tertiary alcohols
Tertiary alcohols are not readily oxidised under similar conditions, as this would involve breaking the carbon skeleton of the molecule, which
requires significantly more energy: no colour change.
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Esterification
Esterification is the combination of carboxylic acid and primary alcohol to produce an ester and water under heat and concentrated sulfuric acid.
Esterifcation giving out water; thus, it is also called condensation. And its reverse reaction is called hydrolysis, with NaOH as an catalyst
H
∣
H − C − Cl
∣
H
The overall reaction with NaOH is:
CH3 Cl + OH − → CH3 OH + Cl−
Using – NH3 can make amine
Using –OH- can make alcohol
Using –CN- can make nitrile
*By adding reducing agent [H], nitrile can be reduced (LiAlH4) to amine with an one unit increase in carbon chain length
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As more and more bromine is added, there could more substitution occurs, but only on 1,3,5 carbon on the benzene ring. The reason behind it is
unnecessary to know for SL.
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Topic 20: Organic chemistry (HL)
20.1 Types of organic reactions
U1 SN1 represents a nucleophilic unimolecular substitution reaction and SN2 represents a nucleophilic bimolecular substitution reaction. SN1 involves a
carbocation intermediate. SN2 involves a concerted reaction with a transition state.
U2 For tertiary halogenoalkanes the predominant mechanism is SN1 and for primary halogenoalkanes it is SN2. Both mechanisms occur for secondary
halogenoalkanes.
U3 The rate determining step (slow step) in an SN1 reaction depends only on the concentration of the halogenoalkane, rate = k[halogenoalkane]. For SN2,
rate = k[halogenoalkane][nucleophile]. SN2 is stereospecific with an inversion of configuration at the carbon.
U4 SN2 reactions are best conducted using aprotic, non-polar solvents and SN1 reactions are best conducted using protic, polar solvents.
U5 An electrophile is an electron-deficient species that can accept electron pairs from a nucleophile. Electrophiles are Lewis acids.
U6 Markovnikov’s rule can be applied to predict the major product in electrophilic addition reactions of unsymmetrical alkenes with hydrogen halides and
interhalogens. The formation of the major product can be explained in terms of the relative stability of possible carbocations in the reaction mechanism.
U7 Benzene is the simplest aromatic hydrocarbon compound (or arene) and has a delocalized structure of π bonds around its ring. Each carbon to carbon
bond has a bond order of 1.5. Benzene is susceptible to attack by electrophiles.
U8 Carboxylic acids can be reduced to primary alcohols (via the aldehyde). Ketones can be reduced to secondary alcohols. Typical reducing agents are
lithium aluminium hydride (used to reduce carboxylic acids) and sodium borohydride.
A1 Explanation of why hydroxide is a better nucleophile than water.
A2 Deduction of the mechanism of the nucleophilic substitution reactions of halogenoalkanes with aqueous sodium hydroxide in terms of SN1 and SN2
mechanisms. Explanation of how the rate depends on the identity of the halogen (ie the leaving group), whether the halogenoalkane is primary, secondary or
tertiary and the choice of solvent.
A3 Outline of the difference between protic and aprotic solvents.
A4 Deduction of the mechanism of the electrophilic addition reactions of alkenes with halogens/interhalogens and hydrogen halides.
A5 Deduction of the mechanism of the nitration (electrophilic substitution) reaction of benzene (using a mixture of concentrated nitric acid and sulphuric acid).
A6 Writing reduction reactions of carbonyl containing compounds: aldehydes and ketones to primary and secondary alcohols and carboxylic acids to aldehydes,
using suitable reducing agents.
A7 Conversion of nitrobenzene to phenylamine via a two-stage reaction.
As the hydrogen atoms are so small, the carbon atom is relatively open to attack by the nucleophile. An unstable transition state is formed in
which the carbon is weakly bonded simultaneously to both the halogen and the nucleophile. The C-X bond breaks heterolytically, which means a
pair of electron is transferred to a single atom, releasing X- and forming the product.
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This is known as a bimolecular reaction because the rate is dependent on both the concentration of the halogenoalkane and of the
hydroxide ion. It is called SN2: substitution nucleophilic bimolecular.
Rate = k[halogenoalkane][nucleophile]
The product is stereo-specific since nucleophile can only attack at the opposite direction of the halogen. It is an inversion of configuration at the
carbon
SN2 reaction is likely to happen in aprotic solvent such as propan-2-one and diethyl ether.
The presence of the alkyl groups around the carbon of the C-X bond causes steric hindrance, meaning that these bulky groups make it difficult
for an incoming group to attack this carbon atom. The first reaction involves the C-X bond breaking heterolytically. The carbon is left with a
positive charge. It is called a carbocation. This is then attacked by the nucleophile in the second step.
A factor which favours this mechanism in tertiary halogenoalkanes is that the carbocation is stabilised by the presence of the three alkyl groups,
as each of these has an electron-donating or positive inductive effect, shown by the blue arrows in the diagram above. This stabilising effect
helps the carbocation to persist for long enough for the second step to occur.
This is a unimolecular reaction. Slow step is the rate determining step.
Rate = k[halogenoalkane]
Since the halogen comes off first, nucleophile can attack the carbocation both from above and below the plane, thus creating a racemic mix with
50% of each enantimers.(inversion and retention)
SN1 reaction prefers protic solvent such as water, methanol and ethanol
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Secondary halogenoalkanes
Secondary halogenoalkanes undergo both SN1 and SN2 mechanisms depending on the solvent and strength of the nucleophile.
Markovnikov’s rule
The rules states “when an unsymmetrical alkene reacts with a hydrogen halide to give an alkyl halide, the hydrogen adds to the carbon of the
alkene that has the greater number of hydrogen substituents, and the halogen to the carbon of the alkene with the fewer number of hydrogen
substituents”
• When a hydrogen halide undergoes eletrophilic addition with an alkene, the carbocation intermediate will form.
• As the double bond of the alkene breaks, it will leave a positive charge on one of two carbons around the double bonds.
• If there is more carbons around the positive charge, this charge can be stabilised around those carbon; thus, this intermediate is more
stable and more likely to be produced
• If there is only a few carbons around the positive charge, this charge cannot be stabilised, leaving the entire molecule unstable and less like
to be produced.
Stabilised by 2 carbons
Stabilised by 1 carbons
Major product Miner product
• This type of electrophilic reaction will create a miner product (2%) and a major product (98%) from different intermediate.
Nitration of benzene
• Benzene is the simplest aromatic hydrocarbon compound (or arene) and has a delocalized structure of π bonds around its ring. Each
carbon to carbon bond has a bond order of 1.5. Benzene is susceptible to attack by electrophiles.
• Benzene reacts with mixture of concentrated nitric acid and sulphuric acid(catalyst) to give nitro benzene
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• Presence of H2SO4 kicks off OH- group on nitric acid to forms water, leaving a NO2+ electrophile
• Electrophile attacks one double bond on benzene ring, giving a intermediate with one positive charge resonating on the ring
• HSO4- attacks hydrogen. Nucleophilic gives electron to the ring to balance the charge.
• H2SO4 is regenerated as a catalyst
• As more and more HNO3 is added, there could more substitution occurs, but only on 1,3,5 carbon on the benzene ring.
• There is partial negative charge (δ-) on the carbon attached to NO2, which induces a partial positive charge (δ+) on the next carbon along
the ring. One partial negative carbon followed by one partial negative carbon.
δ+ δ+
δ-
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The nitrobenzene has been reduced by gaining electrons in the presence of the acid.
The electrons come from the tin, which forms both tin(II) and tin(IV) ions.
Overall
Reduction of alcohol
Carboxylic acids can be reduced to primary alcohols (via the aldehyde). Ketones can be reduced to secondary alcohols. Typical reducing agents
are lithium aluminium hydride(LiAlH4) (used to reduce carboxylic acids) and sodium borohydride(NaBH4)
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20.3 Stereoisomerism
U1 Stereoisomers are subdivided into two classes—conformational isomers, which interconvert by rotation about a σ bond and configurational isomers that
interconvert only by breaking and reforming a bond. Configurational isomers are further subdivided into cis-trans and E/Z isomers and optical isomers.
U2 Cis-trans isomers can occur in alkenes or cycloalkanes (or heteroanalogues) and differ in the positions of atoms (or groups) relative to a reference plane.
According to IUPAC, E/Z isomers refer to alkenes of the form R1R2C=CR3R4 (R1 ≠ R2, R3 ≠ R4) where neither R1 nor R2 need be different from R3 or
R4.
U3 A chiral carbon is a carbon joined to four different atoms or groups.
U4 An optically active compound can rotate the plane of polarized light as it passes through a solution of the compound. Optical isomers are enantiomers.
Enantiomers are non-superimposeable mirror images of each other. Diastereomers are not mirror images of each other.
U5 A racemic mixture (or racemate) is a mixture of two enantiomers in equal amounts and is optically inactive.
A1 Construction of 3-D models (real or virtual) of a wide range of stereoisomers.
A2 Explanation of stereoisomerism in non-cyclic alkenes and C3 and C4 cycloalkanes.
A3 Comparison between the physical and chemical properties of enantiomers.
A4 Description and explanation of optical isomers in simple organic molecules.
A5 Distinction between optical isomers using a polarimeter.
Stereoisomerism
Stereoisomers differ from each other in the spatial arrangement of their atoms. There are two types of stereoisomerism: configurational (rotation
will result in breaking a bond – double bond) and conformational (rotation about aσ bond)
Configurational isomers
When there is some constraint in a molecule that restricts the free rotation of bonded groups, they become fixed in space relative to each
other. This restriction can be caused by a double bond or a cyclic structure. The double bond is made of a σ and a π bond. Rotating would
break the π bond. For cyclic molecules, the substituted groups do not have to be on adjacent carbon atoms – only their position relative to the
plane matters.
Cis/Trans Isomer
Cis means same function groups (hydrogen) around the double bond is on the same side
Trans means same function groups (hydrogen) around the double bond is on the different side
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Physical properties
The physical properties depend on various factors, including:
• the polarity of the molecules
• the shape or symmetry of the molecules
cis-1,2-dichloroethene trans-1,2-dichloroethene
net dipole non-polar molecule
boiling point 60°C boiling point 48°C
melting point -80°C melting point -50°C
The boiling point of the cis isomer is higher because the molecule has dipole-dipole forces of attraction as well as van der Waals’. The melting
point is generally more influenced by the symmetry of the molecules as this affects the packing in the solid state, therefore the trans isomers
has the higher melting point.
*Trans fat has higher melting point and is unhealty
Chemical properties
The chemical properties of geometric isomers are usually very similar. An exception is butenedioic acid.
When the trans isomer is heated it sublimes, but does not react chemically.
E/Z Isomer
Z: highest molecular mass group (higher priority group) is on the same side
E: highest molecular mass group is on the different side
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Z E
Optical isomers have identical chemical and physical properties with two exceptions:
• optical activity
• reactivity with other chiral molecules
Optical activity
Ordinary light consists of electromagnetic waves that oscillate in an infinite number if planes at right angles to the direction of travel. When
passed through a polariser, only the light waves oscillating in a single plane pass through. This is plane-polarised light. The amount and direction
of rotation can be measured with a polarimeter. The light that comes out of the solution passes through a second polariser called an analyser,
which is rotated until the maximum amount of light passes through. In order to compare different solutions, the concentrations, the wavelength of
light used and the sample path-length must all be kept the same.
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Optical isomers rotate plane-polarised light in equal amounts but in opposite directions. A racemic mixture is optically inactive.
Polarimetry can be used to test the purity of chiral compounds.
• Staggered form the protons have space between them so this form is energetically favourable.
• Eclipsed form is energetically unfavourable since there is stereo hindrance among protons.
• Different spatial arrangements due to rotations of groups of atoms about a bond can cause stereo-isomers in non-cylic alkanes.
• This can also happen in cyclohexane – boated shaped and chair shaped cyclohexane.
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Topic 11: Measurement and data processing
11.1 Uncertainty and error in measurement
U1 Qualitative data includes all non-numerical information obtained fromobservations not from measurement.
U2 Quantitative data are obtained from measurements, and are always associatedwith random errors/uncertainties, determined by the apparatus, and by
humanlimitations such as reaction times.
U3 Propagation of random errors in data processing shows the impact of theuncertainties on the final result.
U4 Experimental design and procedure usually lead to systematic errors inmeasurement, which cause a deviation in a particular direction.
U5 Repeat trials and measurements will reduce random errors but not systematicerrors.
A1 Distinction between random errors and systematic errors.
A2 Record uncertainties in all measurements as a range (+) to an appropriateprecision.
A3 Discussion of ways to reduce uncertainties in an experiment.
A4 Propagation of uncertainties in processed data, including the use of percentageuncertainties.
A5 Discussion of systematic errors in all experimental work, their impact on theresults and how they can be reduced.
A6 Estimation of whether a particular source of error is likely to have a major orminor effect on the final result.
A7 Calculation of percentage error when the experimental result can be comparedwith a theoretical or accepted result.
A8 Distinction between accuracy and precision in evaluating results.
Calculating uncertainties
Given a measurement 5 ± 1,
• the absoluteuncertainty is ± 1
• the percentage uncertainty is 20%
When adding or subtracting, the uncertainties are added together.
When multiplying or dividing, percentage uncertainties are added and the result is multiplied by the value to get the absolute uncertainty.
∆A ∆𝐵𝐵
𝐴𝐴 × 𝐵𝐵 = 𝐶𝐶 → ∆𝐶𝐶 = 𝐶𝐶 × � + �
𝐴𝐴 𝐵𝐵
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11.3 Spectroscopic identification of organic compounds
U1 The degree of unsaturation or index of hydrogen deficiency (IHD) can be used to determine from a molecular formula the number of rings or multiple bonds in
a molecule.
U2 Mass spectrometry (MS), proton nuclear magnetic resonance spectroscopy (1H NMR) and infrared spectroscopy (IR) are techniques that can be used to help
identify compounds and to determine their structure.
A1 Determination of the IHD from a molecular formula.
A2 Deduction of information about the structural features of a compound from percentage composition data, MS, 1H NMR or IR.
Mass spectrometry
A mass spectrometer is used to determine relative atomic masses. (Work under a vacuum)
The stages of operation are:
1. Vaporisation: a vaporised sample is injected into the instrument; this
allows individual atoms to be analysed
2. Ionisation: atoms are bombarded with a stream of high energy electrons,
knocking off valence electrons, generating positively charged species
X(g) + e- ---- X+(g) + 2e-
Sample MR
Sample IR spectrometry
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1
H NMR Spectrometry
• Use hydrogen environment to distinguish function group.
• Each bonding structure gives different hydrogen environment
• If identical hydrogen environments bind to different function group, it also those two separate hydrogen environment.
• Label each hydrogen environment (A,B,C….) and count how many hydrogen atoms are in each type of environment.
• The numbers of hydrogen environments are equals to the peaks on NMR diagram.
• Integration number(area under the peak) (trace) is at the bottom of the graph. The ratio between those integration numbers gives the
number of hydrogen per peak.
• Using chemical shift data (in ppm) can identify the hydrogen environment from data booklet.
Sample graph
Hydrogen
Hydrogen Environment C
Environment A
Hydrogen Hydrogen
Environment B Environment C
• Hydrogen environment B and C has the same structure but they attach to different structures (A/D). So they are considered as different
hydrogen environments.
• Therefore, the molecule will have four peaks on NMR.
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Topic 21: Measurement and analysis(HL)
21.1 Spectroscopic identification of organic compounds
U1 Structural identification of compounds involves several different analytical techniques including IR, 1H NMR and MS.
U2 In a high resolution 1H NMR spectrum, single peaks present in low resolution can split into further clusters of peaks.
U3 The structural technique of single crystal X-ray crystallography can be used to identify the bond lengths and bond angles of crystalline compounds.
A1 Explanation of the use of tetramethylsilane (TMS) as the reference standard.
A2 Deduction of the structure of a compound given information from a range of analytical characterization techniques (X-ray crystallography, IR, 1H NMR and
MS).
• All protons are in the same hydrogen environment, so it will give a strong single peak to
signal the zero.
• It is non-toxic and unreactive. So it will not interfere with the sample.
• It is volatile (low boiling point) so it is very easy to be removed.
• It will absorb upfield of protons in NMR, away from most protons in test sample.
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Peak splitting
Number of protons on Sample peak splitting
Number of peaks Type of splitting diagram
adjacent carbon atom (n)
0 1 singlet
1 2 doublet
2 3 triplet
3 4 quartet
X-ray crystallography
• X-ray crystallography can be used to:
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Option D: Medicinal chemistry
D1 Pharmaceutical products and drug action
U1 In animal studies, the therapeutic index is the lethal dose of a drug for 50% of the population (LD50) divided by the minimum effective dose for 50% of the
population (ED50).
U2 In humans, the therapeutic index is the toxic dose of a drug for 50% of the population (TD50) divided by the minimum effective dose for 50% of the population
(ED50).
U3 The therapeutic window is the range of dosages between the minimum amounts of the drug that produce the desired effect and a medically unacceptable
adverse effect.
U4 Dosage, tolerance, addiction and side effects are considerations of drug administration.
U5 Bioavailability is the fraction of the administered dosage that reaches the target part of the human body.
U6 The main steps in the development of synthetic drugs include identifying the need and structure, synthesis, yield and extraction.
U7 Drug–receptor interactions are based on the structure of the drug and the site of activity
A1 Discussion of experimental foundations for therapeutic index and therapeutic window through both animal and human studies.
A2 Discussion of drug administration methods.
A3 Comparison of how functional groups, polarity and medicinal administration can affect bioavailability.
• alters the physiological state, including consciousness, activity level, coordination or cellular chemistry
• alters incoming sensory sensations
• alters mood or emotions
Physiological effects
• Therapeutic effect: the desirable outcome of a pharmaceutical drug on the body
• A drug achieves its therapeutic effect as its molecular structure allows it to bind (through ionic bonding, hydrogen bonding or Van Der
Waal’s forces) with a receptor e.g. a protein molecule such an enzyme or a cellular receptor such as a cell membrane.
• The binding prevents or inhibits the biological activity (e.g. enzyme activity) that allows the disease to develop.
• The receptor part in the molecule or cellular structure is referred to as the site of activity.
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• Identification of ‘lead’ molecule i.e. molecules with a molecular structure that can bind onto the receptor site. Such lead molecules could be
found in plants or microorganisms but often will need to be modified to improve their chemical fit or their bioavailability. Alternatively a lead
molecule is designed using the drug-receptor interactions approach; designing on computers a molecule with a structure that fits chemically
into the receptor site and can bonds with it.
• Using the lead molecule, many different molecules or derivatives are synthesized and their therapeutic effect tested. During this process the
intended molecules are extracted.
• Preclinical trials: testing of medicine in laboratory,
• ‘in vitro’: the lead molecule is tested on animal/human cells and tissues which have been removed from the body and are kept in an
artificial environment.
• ‘in vivo’: testing in live animals (usually 3 different species) to establish ED50 or LD50 which is the amount which kills 50 % of the
population.
• Clinical trials
• Testing of its effectiveness, its therapeutic window, tolerance and its side effects using the placebo effect. This is a ‘blind
trial’ (double-blinded study) in which half of the people/patients involved are given the drug whilst the other half are given a similar
substance that is not the drug (called ‘placebo’ but none of the patients (or even their administering doctors) know which half they
are in.
• Structural modifications likely to be made to, for instance, improve effectiveness or reduce side-effects.
• Submission of reports on the drug and its trials to international or national regulatory bodies.
• Monitoring of the drug after it has been launched; molecule might need further structural changes.
Administering drugs
• oral – taken by mouth, it is very convenient
• inhalation – vapour breathed in; smoking; treatment of respiratory conditions
• skin patches; absorbed directly from the skin into the blood e.g. nicotine patches
• suppositories – inserted into the rectum, it is easy to perform
• eye or ear drops – treatment of infections in those areas
• parenteral (by injection)
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Consideration of drug administration
• Tolerance: Tolerance refers to the body’s reduced response to a drug i.e. its therapeutic effect is less than what it is intended, usually
as a result of taking the drug over a long period of time. As a result more of the drug needs to be taken to achieve the same initial
physiological effect with the danger of exceeding the lethal dose.
• Side effects: Side effects are physiological effects which are not intended and vary greatly from one drug to another, and with the same
drug in different people. Some side effects are beneficial e.g. aspirin, taken for pain relief, helps protect against heart disease. Other drugs
e.g. thalidomide have negative side effects.
• Addiction: Physical dependence. A condition that occurs when a person needs the drug just to live normally and shows withdrawal
symptoms when not taking the drug.
• Dosage: the amount of drug used for each dose and how frequently the drug should be taken. The target of a dosage is to achieve
constant, safe and effective levels of the medicine in blood
humans to determine LD ) 50
• The effectiveness and safety of a drug can be expressed using its therapeutic index (TI)
• The higher the TI, the safer the drug
• Therapeutic Window: the range of doses where the drug provides the desired therapeutic effect without causing unacceptable adverse
effects in most patients. It is between ED50 and TD50
Bioavailability of a drug
• Drug bioavailability: the fraction of administered dose that reaches target part of body
• By definition, intravenous injection has 100% drug bioavailability while other methods of administration decrease in bioavailability
• Bioavailability of pharmaceutical drugs depends on their solubility, polarity, and the presence of certain functional groups. More soluble
with polar groups leads to higher bioavailability.
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D2 Aspirin and penicillin
U1 Mild analgesics function by intercepting the pain stimulus at the source, often by interfering with the production of substances that cause pain, swelling or
fever.
U2 Aspirin is prepared from salicylic acid.
U3 Aspirin can be used as an anticoagulant, in prevention of the recurrence of heart attacks and strokes and as a prophylactic.
U4 Penicillins are antibiotics produced by fungi.
U5 A beta-lactam ring is a part of the core structure of penicillins.
U6 Some antibiotics work by preventing cross-linking of the bacterial cell walls.
U7 Modifying the side-chain results in penicillins that are more resistant to the penicillinase enzyme.
A1 Description of the use of salicylic acid and its derivatives as mild analgesics.
A2 Explanation of the synthesis of aspirin from salicylic acid, including yield, purity by recrystallization and characterization using IR and melting point.
A3 Discussion of the synergistic effects of aspirin with alcohol.
A4 Discussion of how the aspirin can be chemically modified into a salt to increase its aqueous solubility and how this facilitates its bioavailability.
A5 Discussion of the effects of chemically modifying the side-chain of penicillins.
A6 Discussion of the importance of patient compliance and the effects of the overprescription of penicillin.
A7 Explanation of the importance of the beta-lactam ring on the action of penicillin.
Mild analgesics
Mild analgesics, including aspirin, paracetamol, ibuprofen, function by intercepting the pain stimulus at the source, often by blocking the
transmission of pain from source to brain. Prostaglandins are chemicals that send pain impulses to the brain and cause swelling or fever.
Aspirin works by suppressing the production of pain-causing prostaglandins.
Salicylic acid
Salicylic acid is an analgesic that comes from the bark of the willow tree. To reduce its side-effects, OH group was replaced with an ester group
and the compound creates is aspirin. Paracetamol is also salicylic derivatives.
Aspirin Paracetamol
Side-effects stomach wall irritant – stomach ulcer; allergies does not irritate stomach wall
Severe side-effects (over-dosage) Reye’s syndrome in children serious kidney, liver and brain damage
Effects of aspirin
• Relieve pain
• Anticoagulant – stop the blood clotting
• prevention of the recurrence of heart attacks and strokes
• Prophylactic (medicines taken for preventative measures): prevent colon cancer and cardiovascular disease
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Synthesis of aspirin
• OH group was replaced with an ester group in salicylic acid to make aspirin
• Esterification reaction using ethanoic anhydride is taken to make aspirin
• Method
• The 2-hydroxybenzoic acid and ethanoic anhydride are warmed gently with concentrated sulphuric or phosphoric acid as a catalyst.
The mixture is diluted with water and allowed to cool down so that aspirin crystals form as aspirin has a low solubility in water. The
aspirin crystals are removed using filtration
• To increase the yield, the impure crystals are removed using filtration and then dissolved in hot ethanol to make a saturated
solution. This solution is cooled slowly and the aspirin crystalizes again (or recrystallizes) out first (lower solubility of aspirin in
ethanol than the impurities) and is removed using filtration
• Characterization of aspirin
• The identity of the product from the above synthesis can be determined using IR spectroscopy whilst the purity (and therefore the
yield) is determined using melting point determination.
• The aspirin IR spectrum is different from salicylic acid due to the presence of ester group and absence of OH group
Bioavailability of aspirin
• Since aspirin is almost insoluble, its bioavailability is limited
• The solubility and thus bioavailability of drugs can be increase by converting them into ionic salts
• In aspirin, the carboxylic group can be neutralized with sodium hydroxide, producing soluble sodium salt of aspirin
Antibiotics
• Antibacterials are drugs that kill or inhibit the growth of bacteria that cause infectious diseases. An example of antibacterials are penicillins.
• Penicillins are a group of compounds that are produced by fungi and kill harmful micro-organisms; they are therefore called antibiotics.
• Alexander Fleming noticed that a fungus or mould known as Penicillium notatum produced a chemical which inhibited bacterial growth.
• Howard Florey and Ernst Chain isolated penicillin as the antibacterial agent.
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How penecillins work
Its core structure is a four-membered ring consisting of one nitrogen and three carbon atoms and known as beta-lactam ring, which is
responsible for the antibacterial properties. This beta-lactam ring is highly reactive and irreversibly binds to the enzyme transpeptidase in
bacteria. It prevents the development of cross-links in bacterial cell walls This weakens their cell wall causing water to flow into the bacteria
until the water pressure bursts the bacteria open
Human and other animal cells don’t have cell walls therefore are not affected by penicillin
Antibiotic resistance
• Patient compliance: Patient compliance refers to patients not completing the full course of penicillin and this results in prolonging the
disease as not all bacteria are killed. By allowing the bacteria to live longer there can be more mutations eventually producing bacteria with
resistance.
• Overuse of penicillins by humans: Many doctors are too quick to prescribe penicillin. Patients should be encouraged to fight an infection
using their own immune system as overprescription weakens it
• Use of penicillins in animal feedstock as growth promoters: Some penicillins are also effective in animals but they are more often
administered without the animals having any disease; they are administered as a prophylactic to prevent the animals from developing any
disease that could affect their growth. In most cases these penicillins are passed by the animals into the environment and eventually ending
up in the food chain.
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D3 Opiates
U1 The ability of a drug to cross the blood–brain barrier depends on its chemical structure and solubility in water and lipids.
U2 Opiates are natural narcotic analgesics that are derived from the opium poppy
U3 Morphine and codeine are used as strong analgesics. Strong analgesics work by temporarily bonding to receptor sites in the brain, preventing the
transmission of pain impulses without depressing the central nervous system.
U4 Medical use and addictive properties of opiate compounds are related to the presence of opioid receptors in the brain.
A1 Explanation of the synthesis of codeine and diamorphine from morphine.
A2 Description and explanation of the use of strong analgesics.
A3 Comparison of the structures of morphine, codeine and diamorphine (heroin).
A4 Discussion of the advantages and disadvantages of using morphine and its derivatives as strong analgesics.
A5 Discussion of side effects and addiction to opiate compounds.
A6 Explanation of the increased potency of diamorphine compared to morphine based on their chemical structure and solubility.
Opiates
• Opiates, such as morphine, diamorphine (heroin) and codeine, are natural strong analgesics as they reduce severe pain by temporarily
bonding to opioid receptors in the brain or other parts of the central nervous system.
• It will prevent transmission of pain impulses without depressing the central nervous system.
• It is originally derived from the opium poppy plants
• All those three drugs need to be metabolized into morphine before binding to the opiod recepter
• It is the most powerful conscious analgesic
• Opiates are also called narcotics as they act on the brain, are potent analgesics, cause changes in mood and behaviour and can result in
addiction.
• Blood-brain barrier: a series of lipophilic cell membranes that coat the blood vessels in the brain and prevent polar molecules from
entering the central nervous system (CNS)
• To be able to bond with the opioid receptors the opiates need to cross the blood-brain barrier and how well they do this depends on their
solubility in water (blood) and lipids (brain) and on their chemical structure.Strong analgesics
Structure
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Synthesis of codeine
In the synthesis of codeine from morphine one of the hydroxyl groups on the morphine is converted into a methyl ether group through a process
called methylation. This also makes codeine less polar but more lipid soluble although it results in less binding with the opioid receptors –
weaker analgesic.
Advantages Disadvantages
• Strong analgesics and therefore can • Addictive/habit-forming or physical
relieve extreme pain dependence which leads to withdrawal
• Fast acting as can be administered symptoms
intravenously • As heroin is often taken by injections
• Wider therapeutic window/wider safety many addicts get infections such as HIV
margin and hepatitis as a result of sharing
• Relieves anxiety needles.
• Induces relaxation/feeling of well-being. • Tolerance can become an issue with
• High bioavailability. this type of drug as more of the drug
needs to be taken to achieve the same
effect; in order to achieve the desired
effect heroin users may take doses
which exceed the lethal dose.
+ HCl
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D4 pH regulation of the stomach
U1 Non-specific reactions, such as the use of antacids, are those that work to reduce the excess stomach acid.
U2 Active metabolites are the active forms of a drug after it has been processed by the body.
A1 Explanation of how excess acidity in the stomach can be reduced by the use of different bases.
A2 Construction and balancing of equations for neutralization reactions and the stoichiometric application of these equations.
A3 Solving buffer problems using the Henderson–Hasselbalch equation.
A4 Explanation of how compounds such as ranitidine (Zantac) can be used to inhibit stomach acid production.
A5 Explanation of how compounds like omeprazole (Prilosec) and esomeprazole (Nexium) can be used to suppress acid secretion in the stomach.
Indigestion
• A pH of less than 1.0 can also cause ulceration or damage (breaking down of tissue) to the lining of the stomach walls.
• Symptoms of acid indigestion and heartburn can be relieved by either increasing the pH of the stomach by:
• Reducing the effect of the excess acid after it has been released in the stomach by using antacids to neutralize some of the excess
acid.
• Antacids have an immediate effect but only last for a short-term
• Preventing the production of the excess acid by using H2 –receptor antagonists or proton pump inhibitors. Both these antagonists
and proton pump inhibitors take a longer time to provide relief but have a longer term effect. They can also be used to treat ulcers.
Antacids
Antacids are usually weakly basic compounds, often metal oxides or hydroxides, carbonates or hydrogencarbonates, which react with the acid to
produce a salt and water e.g.
Al(OH)3 (s) + 3HCl(aq) → AlCl3 (aq) + 3H2 O(l)
Some antacids use carbonates, which produce carbon dioxide during neutralization, which can cause stomach bloating and flatulence (too much
gas in the stomach). To avert this, antifoaming agents are added such as dimethicone. Some antacids also contain alginates which float to
the top of the stomach, forming a ‘raft’ which acts as a barrier preventing reflux into the oesophagus (heart burn).
Buffer in the stomach
• As antacids are usually weak bases that are added to a strong acid in the stomach a buffer is created.
[salt] [salt]
pH = p𝐾𝐾𝑎𝑎 + log & pOH = p𝐾𝐾𝑏𝑏 + log
[acid] [base]
H2 receptor antagonists
• The acidity of gastric juice can be controlled at cellular level by targeting biochemical mechanisms of acid production
• The secretion of acid in stomach is triggered by histamine binding to H2 receptors in parietal cells of gastric lining
• Ranitidine (Zantac) blocks H2 receptors and reduce secretion of acid. It also provides short term relief of symptoms of indigestion and
require frequent administration
• The drug competes with the histamine to interact with the H2 receptors.
• Using this method have slow effects but effective in the long term.
Active metabolites
An active metabolite is an active form of a drug that has been administered in an inactive form (called prodrug) because of a number of reasons.
The inactive form is then metabolized by the body into its active form (bioactivated) that has a greater therapeutic effect than the inactive form.
Possible reasons for using an inactive form include:
• Has greater bioavailability because it is more soluble or is absorbed faster.
• Easier to administer.
• More selective in its interaction with healthy cells.
• Has fewer side effects linked to the administration.
• Can be stored longer.
• Can withstand different storage conditions.
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D5 Antiviral medications
U1 Viruses lack a cell structure and so are more difficult to target with drugs than bacteria.
U2 Antiviral drugs may work by altering the cell’s genetic material so that the virus cannot use it to multiply. Alternatively, they may prevent the viruses from
multiplying by blocking enzyme activity within the host cell.
A1 Explanation of the different ways in which antiviral medications work.
A2 Description of how viruses differ from bacteria
A3 Explanation of how oseltamivir (Tamiflu) and zanamivir (Relenza) work as a preventative agent against flu viruses.
A4 Comparison of the structures of oseltamivir and zanamivir.
A5 Discussion of the difficulties associated with solving the AIDS problem.
Bacteria Virus
bacteria are self-reproducing i.e. by cell division – do viruses are not self-reproducing as they need a host
not need a host cell to multiply; viruses insert DNA into host cells –
after reproduction the host cell dies
bacteria are able to grow, feed and excrete viruses lack any metabolic functions so they do not
grow, feed or excrete
bacteria contain organelles such as cytoplasm, cell wall viruses consist only of genetic material and protective
and a nucleus which all perform specific functions coating, no cell wall, no nucleus and no cytoplasm
bacteria are (many times) larger than viruses viruses are smaller than bacteria
bacteria mutate/multiply slower than viruse viruses mutate/multiply (much) faster than bacteria
As viruses lack the same cell structures as bacteria, antibacterials are ineffective; in addition viruses also live inside host cells they are also more
difficult to target by drugs.
oseltamivir zanamivir
ether ether
primary amine primary amine
amide amide
ester carboxylic acid
hydroxyl (3)
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Some bacterial resistance More bacterial resistance
Oral Inhalation
HIV/ADIS
• HIV invades white blood cells or CD4+ T cells and causes the disease AIDS that causes the failure of the immune system but this also
allows other life-threatening diseases such as pneumonia and cancer to affect the person carrying the HIV.
• The HIV uses its genetic information in the form of RNA to instruct the while blood cell’s DNA to produce new viral particles.
• HIV is an example of a retrovirus which uses reverse transcriptase to produce DNA strands from their RNA genomes.
Zidovudine
• Since reverse transcriptase is used only by viruses, its inhibition does not affect normal cells
• The antiviral drug called zidovudine uses this technique to combat AIDS and prevent HIV transmission
• However, zidovudine does not eliminate HIV completely, allowing virus to become resistant over time
• Thus, zidovudine is used in combination with other inhibitors to effectively target viruses
• Considering the atom economy in the manufacturing process – making the processes as effective as possible by maximizing raw
materials.
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• Reducing the amount of waste or avoiding waste all together.
• Reduce amount of hazardous waste e.g. reduce use of radioisotopes for instance in diagnostic medicine by using alternatives such
as dyes.
• Safe disposal of waste.
• Using solvents safely in the manufacture or extraction.
• Considering implications to human health of the synthesis and extraction processes.
• Reducing the impact of the pharmaceutical industry on the environment.
Solvent Waste
• The synthesis and extraction of drugs often involves the use of solvents as they can provide a medium in which the synthesis occurs or they
are used to extract the product. (e.g. using solubility) that need to be disposed off at the end of the synthesis or extraction.
• Chlorinated solvents ( CHCl , CCl , CH Cl ) present the hazard of causing ozone depletion and contribute to formation of “photochemical
3 4 2 2
smog”
• Issues with the use of solvents concern:
• Health issues of the solvent itself to the workers e.g. is the solvent carcinogenic or toxic.
• Safety issue with the synthesis or extraction process in which the solvent is used e.g. solvent can be explosive or could form toxic
by-products as a result of the process.
• Environmental impact of solvent use and disposal e.g. emissions in the air and water of chlorinated solvents. Some are toxic to
animals and plants. Greenhouse effect. Flammable.
Nuclear Waste
• Nuclear chemistry is used often in the diagnosis and treatment of diseases and this approach often produces hazardous radioactive waste
that needs to be disposed off.
• Many medicinal procedures involve use of radionuclides which are unstable isotopes of certain elements that undergo spontaneous
radioactive decay
• Ionizing radiation is the hazardous radiation emitted by radioactive materials.
• The radiation can cause changes in DNA, which will lead to cancer development.
• It can also cause reproductive problems in human.
Shikimic acid
• Shikimic acid is the precursor (= a chemical from which a more active chemical is produced) in the production of oseltamivir(Tamiflu) and
is found in low concentrations in a variety of plants.
• For many years shikmic acid was extracted from a natural source but with very low yield.
• Green scientists then produce shikimic acid from E. coli effectively solving shortages of oseltamivir in future
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D7 Taxol—a chiral auxiliary case study (HL)
U1 Taxol is a drug that is commonly used to treat several different forms of cancer.
U2 Taxol naturally occurs in yew trees but is now commonly synthetically produced.
U3 A chiral auxiliary is an optically active substance that is temporarily incorporated into an organic synthesis so that it can be carried out asymmetrically with the
selective formation of a single enantiomer.
A1 Explanation of how taxol (paclitaxel) is obtained and used as a chemotherapeutic agent.
A2 Description of the use of chiral auxiliaries to form the desired enantiomer.
A3 Explanation of the use of a polarimeter to identify enantiomers.
Taxol
• Paclitaxel (Taxol) is a drug used to treat several different forms of cancer
• It is obtained from the bark of pacific yew tree
• However, the yield of taxol from natural yew tree is so low 0.004%.
• Also, it is insoluble, so hard for intravenous injection (into skin)
• Has 11 chiral carbons so extremely difficult to replicate
Semi-synthetic production
• The semi-synthetic method of production taxol used 10-deacetylbaccatin (precursor of taxol)
• 10-deacetylbaccatin production has the yield of 0.2%, which is still 50x higher than extraction from yew tree.
• 10-deacetylbaccatin can be converted to taxol by several synthetic steps including condensation reactions
• For intravenous, a mixture of the drug with chemically modified castor oil and ethanol was diluted with normal saline solution immediately
before injection
Chiral auxiliaries
• Chiral auxiliary is an optically active substance that is temporarily incorporated into an organic synthesis so that it can be carried out
asymmetrically with the selective formation of a single enantiomer
• A chiral auxiliary is used to convert a non-chiral molecule into just the desired enantiomer, thus avoiding the need to separate enantiomers
from a racemic mixture. This is a chiral molecule which binds to the reactant, physically blocking one reaction site through steric
hindrance, so ensuring that the next step in the reaction can only take place from one side. This effectively forces the reaction to proceed
with a specified stereochemistry. Once the specific enantiomer of the new product has been set, the auxiliary can be taken off and
recycled.
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D8 Nuclear medicine (HL)
U1 Alpha, beta, gamma, proton, neutron and positron emissions are all used for medical treatment.
U2 Magnetic resonance imaging (MRI) is an application of NMR technology
U3 Radiotherapy can be internal and/or external.
U4 Targeted Alpha Therapy (TAT) and Boron Neutron Capture Therapy (BNCT) are two methods which are used in cancer treatment.
A1 Discussion of common side effects from radiotherapy.
A2 Explanation of why technetium-99m is the most common radioisotope used in nuclear medicine based on its half-life, emission type and chemistry.
A3 Explanation of why lutetium-177 and yttrium-90 are common isotopes used for radiotherapy based on the type of radiation emitted.
A4 Balancing nuclear equations involving alpha and beta particles.
A5 Calculation of the percentage and amount of radioactive material decayed and remaining after a certain period of time using the nuclear half-life equation.
A6 Explanation of TAT and how it might be used to treat diseases that have spread throughout the body.
Radiation:
Alpha Emitter:
𝟐𝟐𝟐𝟐𝟐𝟐 𝟐𝟐𝟐𝟐𝟐𝟐
𝟖𝟖𝟖𝟖𝐑𝐑𝐑𝐑 → 𝟖𝟖𝟖𝟖𝐑𝐑𝐑𝐑 + 𝟒𝟒𝟐𝟐𝛂𝛂𝟐𝟐+
𝛃𝛃− Emitter
𝟗𝟗𝟗𝟗 𝟗𝟗𝟗𝟗
𝟒𝟒𝟒𝟒𝐓𝐓𝐓𝐓 → 𝟒𝟒𝟒𝟒𝐑𝐑𝐑𝐑 + −𝟏𝟏𝟎𝟎𝛃𝛃−
Half-life
• The amount of time taken for half of radioactive substance to decay
• Denoted as t 1
2
In2
λ=
t1
2
• 𝛌𝛌 – is the decay constant
• Larger decay constant – faster the rate of decaying, meaning the compound has shorter half-life.
t
Nt = N0 (0.5)k
• Nt means the amount of radioactive substance left at time t. N0 means initial concentration. K is the rate constant.
• The equation can also be change to
Nt = N0 e−λt
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Diagnostic techniques in nuclear medicine
• Diagnostic techniques usually involve first attaching a radionuclide(unstable nucleus), known as a tracer, to a biologically active molecule,
making a drug called a radiopharmaceutical.
• Tracer targets specific part of the body. e.g. iodine for the thyroid gland and glucose for the brain
• The tracers used in radiopharmaceuticals must emit gamma rays with enough energy to escape from the body and must have a half-life
just long enough for the scan to be complete before its decay.
𝟗𝟗𝟗𝟗
• The radiopharmaceutical most widely used in diagnosis is technetium-99m, 𝟒𝟒𝟒𝟒 𝐓𝐓𝐓𝐓
• Its half-life is 6 hours, which means that activity in the body stays high for long enough for metabolic processes to be examined by
scanning, but also decays quickly enough to minimize the exposure to the patient.
• Its decay involves the release of gamma rays and low-energy electrons. Without high energy beta emission, the radiation dose is
low. Low-energy gamma rays escape the body and are accurately detected by the gamma camera.
• Technetium is chemically versatile, so acts as a tracer by bonding to a range of biologically active substances. These are
chosen according to the organ to be studied.
10 11
5B + 10n → 5B → 73Li + 42α
• p(A) is the vapour pressure of A over the mixture (partial pressure) at a given temperature
• p*(A) is the vapour pressure over a pure sample of A at the same temperature
• x(A) is the mole fraction of A, which is the ratio of the amount of A to the sum of the amounts of
all components in the mixture
• In the boiling mixture of several substances, the more volatile the molecule is, the easier it will
vapourised.
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• The mixture of liquid will re-condense inside the distillation column. The more volatile molecule will have more mole fraction in the
condensation; thus, it will gain higher partial pressure.
• Overall, the volatile molecule will gradually move up the distillation column.
Breathalyzer
• The simplest breathalyzer consists of a glass tube filled with acidified crystals of potassium dichromate(VI) .
• Alcohol can be oxidized into ethanol or ethanoic acid, which will change the colour of potassium dichromate from orange to green.
• Another type of breathalyzer uses a fuel cell in which ethanol is oxidized at the anode by atmospheric oxygen on the surface of platinum
electrodes.
C2 H5 OH + H2 O → CH3 COOH + 4H + + 4e−
O2 + 4H + + 4e− → 2H2 O
• The electric current produced by the fuel cell is proportional to the concentration of ethanol in the breath
Gas chromatography
• The basic principle is that the components have different affinities for two phases, a stationary phase and a mobile phase
• stationary phase – a microscopic layer of a non-volatile liquid, usually a polymer, which is coated on the walls of an inert solid support
• mobile phase – an inert carrier gas, such as helium
• Separation of the components of a mixture is determined by the different rates at which they move through the instrument
• Depends on boiling points and solubility, molecules partition themselves between two phases.
• Molecule spend more time in gas phase will move faster inside the tube.
• Each component of the mixture will be eluted at a specific interval of time, known as its retention time.
• In some cases, the eluted sample is then analysed by mass spectrum.\
• Gas Chromatography is used to separate different molecules inside a mix sample.
• It can also use retention time to roughly identify a product.
• Together with IR and MS, GS will give a more accurate reading of alcohol level.
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