Professional Documents
Culture Documents
Quelpr CAPE Chemistry Unit 2 Review-Unlocked - 240415 - 095630
Quelpr CAPE Chemistry Unit 2 Review-Unlocked - 240415 - 095630
Alkane Reactions
Alkanes undergo substitution reactions.
• Bond breaking can occur through two methods, homolytic and heterolytic bond
breaking. Homolytic bond breaking is symmetrical, while heterolytic bond breaking is
unsymmetrical.
Note the difference in arrows used! One-headed ‘fishhook’ arrows are used to show homolytic
bond breaking while double headed arrows are used to show heterolytic bond breaking.
Halogenation
• Halogenation is the substitution of a hydrogen atom of an alkane with a halogen.
o This occurs through free radical substitution.
• Free radical substitution relies on the high reactivity of radicals (species carrying an odd
number of electrons).
• Radicals can abstract an atom from a molecule. Abstraction is the removal of an atom
or group from a molecule by a radical.
• The halogenation reaction has three stages (using chlorine as an example):
Initiation
Irradiation of the halogen with UV light initiates the homolytic breakage of the covalent bond in
some of the halogen molecules. A few halogen radicals are formed.
Propagation
A reactive halogen radical collides with a molecule of the alkane, abstracting a hydrogen atom
from it to produce the hydrogen halide and an alkyl radical.
The alkyl radical goes on to react with another halogen molecule, releasing a halogen radical and
forming a haloalkane. The halogen radical goes on to continue propagation, leading to a chain
reaction.
Termination
When two radicals collide, they can form a bond and end a reaction cycle, ending the chain
propagation. As the number of radicals at any time is very small, these reactions are infrequent.
Cracking
• Cracking involves the breakdown of saturated hydrocarbon molecules (alkanes) into
smaller (usually more useful) products (e.g. a smaller alkane and alkene) through the
application of heat, pressure and catalysts.
• Thermal cracking utilizes high temperatures (450-750°C) and pressures (up to 70 atm)
o Thermal cracking operates through free radical mechanisms.
• Catalytic cracking utilizes zeolites (complex aluminosilicates of the form Al2O5Si
associated with positive ions) along with lower temperatures (~500°C) and moderately
low pressures.
o The mechanism includes ionic intermediates.
• Note that cracking occurs in a fairly random manner, with only relative proportions of
alkenes to alkane products being generally modifiable based on conditions.
Combustion
• Combustion reactions are exothermic reactions of hydrocarbons with oxygen to produce
carbon dioxide and water (complete combustion) and occasionally carbon monoxide and
carbon as well (incomplete combustion).
• Complete combustion reactions follow a fairly repetitive equation structure as follows:
𝑦 𝑦
𝐶𝑥 𝐻𝑦 + (𝑥 + ) 𝑂2 → 𝑥𝐶𝑂2 + 𝐻2 𝑂
4 2
Alkene Reactions
• Alkenes are more reactive than alkanes due to the presence of a carbon-carbon double
bond.
• The electrons of the 𝜋 molecular orbital are of a higher energy than those of the 𝜎
molecular orbital. Alkanes are less reactive than alkenes because they lack this more
reactive bond.
• The 𝜋-bond of the alkene can act as a nucleophile, donating electrons to electrophiles in
electrophilic reactions.
o Unsurprisingly, alkenes undergo electrophilic addition reactions, where a
molecule is added across the double bond, giving a single product.
With Br2(l)`
• This reaction involves the addition of bromine dissolved in an organic solvent (like
tetrachloromethane, CCl4) to an alkene (like ethene)
• The product is a vicinal dihaloalkane (a dihaloalkane with both halogen substituents on
adjacent carbons). Here it is 1,2-dibromoethane.
A dipole is induced in the highly polarizable bromine molecule by the electron rich 𝜋 bond.
The partially positive bromine acts as an electrophile, attacking the double bond.
The result is the bromonium ion.
The remaining bromide ion attacks the bromonium ion from the opposite side, compensating for
the positive charge.
• The bromine starts out as red-brown but becomes decolorised throughout the reaction.
With Br2(aq)
• When an alkene reacts with bromine dissolved in water, the result is a bromoalkanol and
HBr, where the bromine substituent and the hydroxyl group are on adjacent carbons
(across the double bond).
o The reaction mechanism is similar to the previous one except that water becomes
attracted to the intermediate bromonium instead of the bromide ion.
o The OH- from the water combines with the bromonium instead, releasing a proton
which combines with the remaining bromide ion.
• The bromine water starts out as brown but becomes decolorised throughout the reaction.
The identities of R1 R2, R3 and R4 dictate the outcome of the following steps.
Stage 2: Further oxidation
If a product is a ketone (both R groups attached to the carbonyl group are alkyl groups), it will
not undergo further oxidation.
If a product is an aldehyde (one of the R groups on the carbonyl group is a hydrogen), it will be
further oxidized to a carboxylic acid.
But actually, the methanoic acid is further oxidized to carbon dioxide and water:
Reactions of Alcohols
• An alcohol is designated as primary, secondary and tertiary based on the number of
carbons to which the carbon carrying the hydroxyl group is joined (just like the
carbocations).
o The following reactions can follow different mechanisms or outcomes based on
the type of alcohol we are using in the reaction.
Hydrolysis
• Usually alkaline hydrolysis, which requires an alkaline solution like NaOH(aq)
• The products of this reaction are an alcohol and the hydrohalic acid (the hydrogen halide
dissolved in water)
• Primary (and usually secondary) haloalkanes undergo a particular mechanism called
SN2 (short for substitution, nucleophilic, bimolecular).
o Substitution- The halogen substituent is being substituted by a hydroxyl group.
o Nucleophilic- A nucleophile (electron rich/negatively charged species) initiates
the reaction
o Bimolecular- TWO molecules are involved in the rate determining step.
o In this mechanism, bond breaking and making occurs in a concerted manner,
and both occur at the same time with the formation of a transition state.
Step 2: The cyanide ion acts as a nucleophile, attacking the partial positive charge on the carbon
of the carbonyl group. The pi bond is broken and the cyanide joins the chain as an extra carbon
with a nitrile group.
Reduction
• Reduction of carbonyl compounds is basically the addition of a hydrogen atom (an
electron is gained).
o This reduction can occur through the usage of different reagents including H2/Pt
(hydrogen gas over a platinum catalyst), LiAlH4 (lithium
tetrahydridoaluminate) or NaBH4 (lithium tetraydridoborate)
o Aldehydes are reduced to primary alcohols while ketones are reduced to
secondary alcohols.
Using LiAlH4
• This reducing agent is more reactive than NaBH4.
• The reaction is usually carried out in carefully dried ethoxyethane (diethyl ether) because
it reacts violently with water and alcohols.
• An acid is added to the reaction mixture afterwards to release the alcohol from a complex
ion.
Using NaBH4
• This is a gentler reducing agent.
• The reaction is carried out with the carbonyl compound dissolved in an alcohol.
Qualitative Tests
The following reactions allow us to distinguish between aldehydes, ketones and other organic
compound based on the observations.
Tollens’ Reagent
Silver mirror formed on
(Diamine silver (I) No reaction
reaction container
hydroxide)
No reaction (mixture remains
Fehling’s Solution Red precipitate formed
deep blue)
Diute Acidified
Change from purple to No reaction (mixture remains
Potassium Manganate
colourless purple)
(VII)
With NaOH
• The result is the formation of an alkanoate/carboxylate salt,
that is, the hydrogen ion is substituted for a sodium ion, along
with water.
• It is a neutralization reaction, giving a salt and water.
With NaHCO3
• The result is the same as above except with the added product of carbon dioxide.
Metals
• The result is a carboxylate salt and hydrogen gas. The metal must be above hydrogen in
the reactivity series (remember that?), so no reaction with copper.
• Acid hydrolysis produces the carboxylic acid and alcohol without any production of salt.
• The ester is heated with an acid.
• The alkoxy group is an alkyl group bonded to an oxygen atom, or an alkanol with the
hydrogen removed.
o Note that only the portion of the ester originating from the alcohol can exchange
with the alcohol. The central carbonyl group and the alkyl group from the
carboxylic acid cannot participate.
• When transesterification is carried out between a
triglyceride and an alcohol (with the help of an NaOH
catalyst), the result is an acyl ester and glycerol. The
acyl ester is used as a biodiesel.
• When a primary amine reacts with a carboxylic acid however, the result is an amide.
Reactions of Benzene (and Methylbenzene/Toluene)
• Benzene actually undergoes electrophilic substitution reactions, contrary to the
addition reactions that would be expected of an unsaturated carbon compound. This is
due to the delocalization of electrons in the Benzene ring.
• Benzene and methylbenzene (also called toluene) undergo the same kind of reactions, as
they are of similar reactivities (despite toluene being slightly more reactive thanks to the
electron donating methyl substituent, but we’ll get to that later).
Halogenation (Br2/FeBr3)
• In this reaction, FeBr3 (or AlBr3) acts as a Friedel-Crafts Catalyst.
• Halogenation using another halogen, like chlorine, follows a similar pattern.
o The catalyst would be FeCl3 or AlCl3.
The reaction is essentially the same for toluene.
Reactions of Phenol
With Acyl Halides
• Phenol reacts with acyl halides to form an ester and the hydrogen halide.
A brief aside on activating and deactivating groups, and inductive and resonance/conjugative
effects:
• Activating groups are electron donating groups, meaning that they donate electrons to
the benzene ring, increasing the electron density of the ring, stabilizing the carbocation
intermediate (lowering the activation energy for its formation) and increasing the
likelihood of electrophilic attack.
• Deactivating groups are electron withdrawing groups, meaning that they pull electrons
from the benzene ring, decreasing electron density of the ring, destabilizing the
carbocation intermediate (increasing the activation energy for its formation) and
decreasing the likelihood of electrophilic attack.
Diazotization (NaNO2/HCl)
• The reaction produces benzene diazonium chloride, sodium chloride and water.
o This occurs at 0-5°C, as diazonium salts will decompose at higher temperatures to
form phenol, nitrogen gas and a proton.
• Technically, the sodium nitrite and hydrochloric acid react to form nitrous acid, which
then goes on to react with the aniline molecule.
Coupling (with Diazonium Salt)
• If we take a diazonium salt like the one formed above and mix it with phenol in an
alkaline medium (i.e. solution containing NaOH), the result will be coupling to form an
azo compound.
o HCl is also formed as the chloride ion is released.
o The NaOH is necessary to convert the phenol to the phenoxide ion, which can
then go on to react with the salt.
o The reaction also occurs at 0-5°C due to the volatility of the reactants.
As shown above, the reaction also occurs between aniline (phenylamine) and the benzene
diazonium chloride salt, forming a yellow dye instead.
• When an electron donating group (EDG) is added, the acidity decreases (pKa
increases).
o For example, alkyl groups are EDGs. As such, tertiary alcohols are weaker than
secondary alcohols, which are weaker than primary alcohols.
Phenol Acidity
• Phenol is more acidic than aliphatic alcohols (by about a million times).
o The phenoxide ion is more stable than any alkoxide ion due to the presence of the
aromatic ring.
o The negative charge on the oxygen atom of the phenoxide ion is delocalised
around the ring.
▪ One of the lone pairs of the oxygen overlaps with the band of delocalized
electrons on the benzene ring, resulting in a delocalisation of the negative
charge.
▪ Electron density is moved away (on average) from the hydrogen atom due
to the electron donating resonance effect of the hydroxyl group, further
straining the bond, and increasing the likelihood of dissociation.
• The substituent attached to the phenol also
affects the acidity.
• Electron withdrawing groups take
electron density away from the benzene
ring, in turn reducing electron density in
the benzene ring and in the O-H bond. The hydrogen atom thus requires less energy to
dissociate.
• The C-O 𝜋 bond overlaps with the p orbital of the other oxygen, forming a delocalized
electron band.
o Formation of this ion requires less energy and is more favourable.
• In addition, while in the molecular form, the electronegative oxygen in the carbon-
oxygen double bond exerts an electron withdrawing inductive effect, decreasing electron
density in the O-H bond.
o This weakens the bond, making it easier to break.
Chlorosubstituted Acids
• Chlorosubstituted carboxylic acids are those with a chlorine substituent.
• Chlorine (and any halogen substituent) is strongly inductively electron withdrawing
substituent, and as such will intensify polarization elsewhere in the molecule
• Chlorosubstituted carboxylic acids are stronger acids, as the electronegative halogen
substituent will pull electron density away from the COO- group, further delocalising the
negative charge and increasing the stability of the ion.
• The pulling of electron density will also weaken the OH bond in the molecular form,
making the bond easier to break.
Aside: Why would ethanoic acid still be a stronger acid than phenol?
• The question arises since both molecules exhibit some resonance effects resulting in the
delocalization of a negative charge on oxygen.
• However, look at the atoms over which the charge is delocalized.
o In phenoxide ion (formed by dissociation of phenol), those atoms are carbon
atoms in the benzene ring. The oxygen carrying the charge is still the most
electronegative and will attract the electrons most strongly. The negative charge
will still be more concentrated on this atom, making it more likely to attract
hydrogen and reform phenol.
o In ethanoate (or any carboxylate ion), the negative charge is delocalised over a
carbon atom and another oxygen atom. Charge is more evenly distributed and
less concentrated, increasing its stability and decreasing the likelihood of
reformation of the carboxylic acid.
Aliphatic Amines
• Amines are basic due to the lone pair available on the nitrogen atom which is available
for accepting protons.
o As such, anything that increases the availability of the lone pair on the nitrogen
atom increases its strength as a base.
• The degree of substitution of an amine influences its strength as a base. Remember that
alkyl substituents are EDGs, and their positive inductive effect will push electron
density towards the nitrogen, making the nitrogen’s lone pair more available to form
dative covalent bonds with protons.
Aromatic Amines
• Arylamines/Aromatic Amines are less basic
than alkylamines/aliphatic amines because the
nitrogen lone-pair electrons are delocalized
by interaction with the aromatic ring’s 𝝅
electron system and are less available for
bonding to H+.
• Activating groups, or electron donating
groups, increase the electron density of the
benzene ring and the 𝝅 electron system.
• This increases the availability of the lone pair
on the nitrogen of the amine substituent, allowing it to accept a proton.
Amides
• Amides are less basic than both aromatic and aliphatic
amines.
• The lone pair on nitrogen is delocalised (conjugative
effect). This orbital overlaps with the adjacent 𝜋 bond
electrons, forming a delocalised band.
o The lone pair becomes less available to accept
protons.
Amino Acids
• These are organic compounds containing an amine group and a carboxylic acid functional
group.
• The carboxylic acid group is deprotonated to the
carboxylate anion, while the amine group is protonated
and exists as the ammonium cation.
o Amino acids exist in solution primarily as dipolar
ions, also called inner salts or zwitterions.
o A zwitterion is a molecule containing an equal
number of positively and negatively charged functional groups. They have both
an intramolecular positive and negative charge (which are equal in magnitude).
o Amino acids are amphiprotic, meaning they can both accept and donate
electrons.
• In aqueous acid solution, an amino acid zwitterion is a base that accepts a proton onto
its CO2- group to yield a cation.
• In aqueous base solution, the zwitterion is an acid that loses a proton from its NH3+
group to form an anion.
Macromolecules
• A macromolecule is a large molecule comprising a large number of atoms.
• A polymer is a macromolecule comprised of many identical or similar molecular
subunits known as monomers arranged in a regular, organized manner.
• Polymerization is the process by which many small molecules called monomers are
combined to produce a polymer.
o The two types of polymerization are:
o Addition polymerization, where monomers combine without the loss of atoms or
the formation of by-products.
o Condensation polymerization, where monomers combine with the loss of atoms
or a small molecule (eg HCl, H2O)
Addition Polymerization
• Characteristics:
o All monomers are the same.
o The empirical formula of the polymer is the same as the monomer as no atoms
are lost during formation.
o The polymer is the only product formed.
Formation of Polyethene
• The polymerization of ethene is described via a radical process, that is, initiation,
propagation and termination, as with radical substitution of alkanes.
• Involves the use of a Ziegler-Natta Catalyst and high pressures.
o Two forms of polyethene are possible:
▪ Low density polyethene is formed using high pressure and high
temperature. Used in plastic bags and insulation cables.
▪ High density polyethene is formed using lower temperatures and
pressures. Used in buckets and bottles.
• A chain initiator radical (usually oxygen) reacts with ethene to form a new radical
• Chain propagation occurs via the reaction of this new radical with another ethene
molecule.
Polytetrafluoroethene (PTFE)
• PTFE (also called Teflon) is formed from
several tetrachloroethene monomers, and is
used in non-stick coatings and insulation
Condensation Polymerization
• Characteristics:
o Always forms two products, the polymer and a small molecule.
o The polymer is either a copolymer (a polymer produced from two or more
monomer species), or produced from monomers with two different functional
groups.
o The empirical formula of the polymer is different from the monomer.
o The monomers must have two functional groups.
• The two most important reactions of condensation polymerization are:
o The formation of an amide from the reaction between a carboxylic acid group
and an amine group.
o The formation of an ester from the reaction between a carboxylic acid group and
a hydroxyl group.
Uncertainty in Measurements
A Few Definitions
• Calibration is the comparison of an instrument’s performance to a standard of known
accuracy.
o It is also the act of checking or adjusting (by comparison with a standard) the
accuracy of a measuring instrument.
• Detection Limit of an instrument is a measure of the smallest concentration/value
which can be determined with a specified precision or reproducibility.
• Sensitivity of an instrument related to how the variation in the output of that instrument
can be apportioned, qualitatively or quantitatively to different sources of variation.
pH at
Suitable
Acid Strength Base Strength Equivalence
Indicator
Point
Bromothymol
Blue, Phenol
Strong Strong 7
Red,
Phenolphthalein
Strong Weak <7 Methyl Orange
Weak Strong >7 Phenolphthalein
None- use back
Weak Weak Variable
titration instead
o pH Meter- The actual pH of the reaction mixture can be detected and plotted
using a pH Meter. This is called a potentiometric titration.
o Conductometer/Electrical Conductivity Meter- a
conductometer can be used to measure the conductivity of
the reaction mixture throughout the titration. Conductivity
decreases to a minimum at the equivalence point, as all
the ions in solution have reacted, leaving only slightly
ionizable water.
▪ This is called a conductimetric titration.
o Thermometer- Neutralization reactions are exothermic, and as such, the
temperature of a reaction mixture will reach a maximum at the equivalence point.
▪ This is called a thermometric titration.
Back Titrations in Acid/Base Analysis
• Back titration (or indirect titration) is a method where an analyte is added to a solution
containing an excess of standard.
o The quantity of unreacted standard is then quantified by titration against a
second standard.
o The quantity of the first standard which has reacted is calculated through
subtraction, and the quantity of the analyte can be calculated through knowledge
of the reaction.
• When is back titration used?
o The analyte is insoluble in water
o The analyte is volatile
o The reaction between analyte and standard is slow
o A direct titration would be a weak acid/weak base titration, where the end point
is not sharp.
Primary Standards
• These are compounds which meet the following criteria:
o Stable, so that it can be easily weighed under atmospheric conditions and not
change during storage.
o Easy to obtain in highly purified form
o Soluble in the titration medium in which it is to be used
o High formula weight to reduce weighing errors
o The reaction between the primary standard and the compound being standardized
should be fast and quantitative (go to completion)
o Inexpensive
• For standardization of acids:
o Na2CO3
o NaHCO3
• For standardization of permanganate solutions:
o Oxalic Acid - (COOH)2
o Sodium Oxalate – (COONa)2
• For standardization of thiosulfate solutions:
o Potassium Iodate - KIO3
Redox Titrations
• In a redox reaction, one reactant is oxidized and the other reactant is reduced.
o Analytes which are readily oxidized or reduced can be analysed quantitatively by
titrimetric analysis, where the standard is an oxidizing or reducing agent.
Potassium Permanganate
• Acidified MnO4- solution is a strong oxidizing agent, where manganese (VII) accepts 5
electrons and is reduced to manganese (II)
𝑀𝑛𝑂4− + 8𝐻 + + 5𝑒 − ↔ 𝑀𝑛2+ + 4𝐻2 𝑂
• The permanganate ion is deep purple, and so titrations with colourless or faintly
coloured analytes do not require indicators, they are self-indicating.
• Potassium permanganate is not a primary standard, as it is contaminated with an
insoluble brown solid manganese dioxide (MnO2)
o Potassium permanganate must first be standardized before usage, usually with
sodium oxalate.
Iodometric Titrations
• Iodine (I2) is an oxidizing agent and readily takes two electrons from a reducing agent to
form two iodide ions.
• Iodine is soluble in fairly concentrated solutions of potassium iodide, where the triiodide
ion is formed:
o 𝐼2 + 𝐼 − ↔ 𝐼3−
o Triiodide is also an oxidizing agent and is reduced by two electrons to form three
iodide ions
o Iodine tends to evaporate when in aqueous solution, but this problem is avoided
when iodine is dissolved in potassium iodide solution and the triiodide ion forms.
• Starch is the indicator for titrations involving iodine.
o I2 dissolved in KI is red. When dilute starch solution is added, it becomes deep
blue.
• Iodine solutions are commonly standardized using sodium thiosulfate.
o Na2S2O3 is not a primary standard as it is commonly a pentahydrate but is
efflorescent, so it also loses water.
o Sodium thiosulphate is standardized using the primary standard potassium iodate
(in acid solution).
Preparing a standard solution
Gravimetric Methods of Analysis
• Gravimetric analysis is quantitative analysis by weight.
o It involves isolating and weighing an element or a definite compound of the
element in as pure a form as possible.
o Usually, the element to be determined is transformed into a pure stable compound
which can be readily converted into a suitable form for weighing.
• Advantages of Gravimetric analysis:
o It is accurate and precise with modern analytical balances
o Possible sources of error can be easily checked (precipitates may be examined for
impurities, and filtrates can be tested for completion of precipitation)
o It involves direct measurement, so no calibration is required. It is an absolute
method.
o It is inexpensive to carry out (can sometimes only require a crucible and heat)
Precipitation Method
• The constituent being determined is precipitated from solution in a form which is so
slightly soluble that no appreciable loss occurs when the precipitate is separated by
filtration and weighed.
• Requirements for the precipitation:
o The precipitate must be so insoluble that no appreciable loss occurs when it is
collected by filtration. The quantity remaining in solution does not exceed the
minimum detectable by the ordinary analytical balance.
o The precipitate must be granular; the size of the particles must be sufficiently
large so that they do not pass through the filtering medium and are not diminished
by the washing process.
o The precipitate must be convertible to a pure substance of definite chemical
composition (such as through evaporation)
• Apparatus for gravimetric analysis:
o Analytical Balance: a balance for determination of weights to 4dp
o Laboratory Oven: for drying reagents and precipitates
o Desiccators: a large glass vessel in which a drying agent (like silica gel or CaCl2)
is placed.
o Weighing paper
o Vacuum Source: an aspirator pump or
water pump
o Sintered Glass Crucibles, porosity #4:
cylindrical glass funnel used for filtration
and weighing.
▪ The base is a porous disc which has
been subjected heat and pressure.
o Suction/Buchner funnel
o Suction filter flask
Volatilization/Evolution Methods
• These methods depend essentially upon the removal of volatile constituents, which can
happen in several ways, including heating/ignition and treatment with a chemical
reagent which renders a constituent volatile.
o The determination of the amount of water of crystallization in a hydrate can
occur by heating a sample of the hydrated salt in a silica crucible and recursively
weighing the residue until a constant mass is reached.
o The purity of a carbonate compound can be determined by reacting the
compound with excess acid. This reaction releases gaseous carbon dioxide.
▪ The evolved CO2 is made to react with an absorbent like NaOH. The
change in mass of the absorbent is used to determine the quantity of carbon
dioxide that has reacted.
• In all compounds (except alkanes), electrons may undergo several possible transitions
of different energies:
However, only the bottom three are actually within the UV-Vis region: 𝒏 → 𝝅∗ , 𝒏 →
𝝈∗ and 𝝅 → 𝝅∗ .
(𝜎 𝑡𝑜 𝜋 ∗ is impossible based on selection rules)
Why aren’t some compounds UV/Vis active?
• To say some compounds are not UV/Vis active is to say that they do not absorb light in
the ultraviolet-visible region of the electromagnetic spectrum.
• Above, the important transitions involve 𝝅 antibonding orbitals and non-bonding
orbitals. As such, if a compound does not have either 𝝅 bonds or lone pairs, they will
not absorb in the UV/Vis region.
o UV/Vis inactive compounds include alkanes which lack both pi bonds and lone
pairs.
• Compounds which absorb in the UV/Vis region contain certain groups called
chromophores or lone pairs of electrons.
o Chromophores are groups in a molecule producing absorption of light.
o These include the carbon-carbon double bond, carbonyl group, amide group,
amine group, carbon-carbon triple bond, acyl chloride group and nitro group
Beer-Lambert’s Law
• The greater the number of molecules capable of absorbing light of a given wavelength in
solution, the greater the extent of light absorption.
o And the more effectively a molecule absorbs light of a given wavelength, the
greater the extent of light absorption.
o As such, the concentration of a molecule and the identity of the molecule in
solution affect the extent of light absorption.
• There are two empirical laws which describe the absorption of light by compounds in
solution:
o Lambert’s Law- the fraction of incident light absorbed by a homogenous liquid
depends on the length of the absorbing medium, also called the path length (l).
o Beer’s Law- the fraction of incident light absorbed by a homogenous liquid is
proportional to the number of absorbing molecules
o The combination of these laws is the Beer-Lambert Law, which states:
𝐼
▪ 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒 (𝐴) = log10 𝐼0 = 𝜀𝑐𝑙
▪ Where 𝐼0 is incident light intensity, 𝐼 is intensity of transmitted light, 𝜀 is
molar extinction coefficient, c is concentration and l is path length
• For UV/Vis spectroscopy, the source of UV light is a deuterium discharge lamp.
o The source of visible light is a tungsten filament lamp.
• The sample for analysis is usually dissolved in a solvent which does not absorb light at
the same wavelength as the sample. This is usually ethanol, water or hexane.
• The sample is typically placed in a glass, quartz (transparent down to 200nm) or
calcium fluoride (transparent down to 100nm) cuvette and placed in the relevant slot of
the spectrophotometer.
Infrared Spectroscopy
Infrared Absorption Process
• The absorption of infrared radiation is, like other absorption processes, a quantized
process.
• The frequencies of infrared radiation that match the natural vibrational frequencies of
the bonds of the molecule in question are absorbed, and this energy increases the
amplitude of the vibrational frequencies of the bonds in most covalent molecules.
o Only those bonds that have a dipole moment that changes as a function of time
are capable of absorbing infrared radiation.
o A bond must present an electrical dipole that is changing at the same frequency
as the incoming radiation for energy to be transferred.
• Since every bond has a different natural frequency of vibration, and because two of the
same bond exist in different environments in two different compounds, no two molecules
of different structure have exactly the same infrared spectrum.
• Infrared spectra also allow us to determine structural information about a molecule- that
is, we can infer the functional groups present in
a molecule based on the peaks in the infrared
spectrum, as certain types of bonds will exhibit
similar absorptions.
• As seen on the right, IR spectra are usually
plotted as transmittance (amount of light passing
1
through) against wavenumber (𝜆 (𝑖𝑛 𝑐𝑚))
• There are different modes of vibration, that is,
molecules can undergo a set of either stretching or bending vibrational motion which
can be infrared active.
o If a vibrational mode is infrared active, it means that the dipole moment of the
molecule changes as a result of this motion over time.
o This can only occur in polar molecules, and excludes non-polar molecules like
N2 or Argon.
Preparation of A Sample
Solids
KBr pellet
• Mix the finely ground sample with powdered KBr (potassium bromide)
• Press the mixture under high pressure.
o The KBr melts at high pressure and seals the sample into a matrix.
• The resulting KBr pellet is placed into the instrument.
o KBr is used since it is IR transparent down to 400cm-1,
which is just at the lower end of the range of detection
for most IR spectrophotometers.
OR the Nujol mull
• The compound is ground with Nujol (mineral oil) to create a
suspension of the sample dispersed in the oil.
• The suspension is then placed between two KBr or NaCl plates.
o This method is disadvantageous as the mineral oil is IR
active at 2924, 1462 and 1377 cm-1.
Liquids
• A drop of liquid organic compound is placed between two polished NaCl of KBr plates,
then pressed gently to form a thin liquid film between the plates.
• The compound must be free of water.
In modern FT-IR spectrometers, the sample does not need to be prepared, and can simply be
placed on an ATR (attenuated total reflection) crystal made of diamond, zinc selenide or
germanium.
Infrared Absorption and the Environment
• Radiation from the Sun which reaches the Earth’s atmosphere is approximately 3% UV
light, 44% visible light and 53% infrared light. The visible radiation is absorbed by
the Earth’s surface.
o This absorption of energy warms the surface, and the surface then emits lower
energy IR radiation back towards space.
• The gases nitrogen, oxygen and argon make up more than 99% of the Earth’s
atmosphere. These gases do not absorb either visible or infrared radiation as they are
completely non-polar.
• However, the small percentages of carbon dioxide and water vapour present in the
atmosphere absorb the infrared radiation from the Earth’s surface. This causes heating of
the atmosphere, and also makes the surface of the Earth warmer.
o This heating is known as the greenhouse effect- greenhouse gases trap some of
the heat radiated from the earth’s surface.
o Greenhouse gases include carbon dioxide, methane and nitrous oxide, all of
which are IR active.
Mass Spectroscopy
Principles
• Know the diagram on the right, it is a block
diagram representing mass spectroscopy.
• The mass spectrometer has five
components:
o Sample Inlet brings the sample from the lab to the low pressure spectrometer.
o Ion Source where sample molecules are transformed into gas phase ions. These
are then accelerated under a magnetic field.
o Mass analyser separates sample ions based on their mass-to-charge (m/z) ratio.
o Detector counts the ions
o Data system records and processes the output to produce a mass spectrum, a
graph of relative abundance versus m/z ratio.
• Ions are usually produced through electrical ionization.
o A beam of high-energy electrons is emitted from a filament that is heated to
several thousand degrees Celsius.
o These high-energy electrons strike the stream of molecules that has been
admitted from the sample inlet system.
o The electron–molecule collision strips an electron from the molecule, creating a
cation.
o A repeller plate, which carries a positive electrical potential, directs the newly
created ions toward a series of accelerating plates. A large potential difference,
ranging from 1 to 10 kilovolts (kV), applied across these accelerating plates
produces a beam of rapidly traveling positive ions.
o One or more focusing slits direct the ions into a uniform beam
• The ions are accelerated and pass into the mass analyser (usually a magnetic sector mass
analyser), where they are separated according to the m/z ratio
𝑚 𝐵2 𝑟 2
o = , describes the path taken based on this ratio and the strength of magnetic
𝑧 2𝑉
field (B) or potential difference (V).
• The most abundant ion formed in the ionization chamber gives rise to the tallest peak in
the mass spectrum, called the base peak. This peak is assigned 100% relative
abundance.
o The molecular ion (𝑴+• ) is the radical cation formed from the removal of an
electron from the molecule in study.
▪ The heaviest peak (highest m/z ratio) is usually the molecular ion.
▪ Molecular ions tend to be unstable, and break down into fragments of
smaller mass. As such, the molecular ion does not tend to be the base
peak.
▪ The molecular ion will have the same mass as the compound being
analysed.
▪ Sometimes the molecular ion is so unstable that it is not detected (it
breaks down before reaching the detector)
Mass Spectra
• If mass spectroscopy is carried out on a sample of a single species atoms (one element),
the peaks will correspond to isotopes of the element.
o Ionizing the atoms will produce cations with an m/z ratio corresponding to the
mass of the isotope (as the ions have majorly +1 charge).
• As you can see in the table above, both of the halogens have major isotopes separated by
2 atomic mass units.
o As such, two peaks with different isotopes would also be separated by 2 m/z units.
o The peak 2 m/z units to the right of the molecular ion peak is called the M+2
peak.
o Based on the ratio of abundance between the M+ and M+2 peaks, we can infer the
presence of chlorine or bromine.
▪ If chlorine is present, the M+ will be 3 times taller than M+2
▪ If bromine is present, the M+ and M+2 will be approximately the same
heights
Fragmentation Patterns
• The electron beam is energetic enough to displace electrons from the molecules, but it is
also capable of breaking some of the bonds in the molecule.
• The positively charged fragments are also accelerated in the ionization chamber, sent
through the analyzer, detected, and recorded on the mass spectrum.
o These fragment ions appear at m/z values corresponding to their individual
masses.
• They can also be produced if the molecular ion has a shorter lifetime that 10-5 seconds
(the radical cation disintegrates)
The Nitrogen Rule
• This rule states that if a compound has an even number of nitrogen atoms (including
zero), its molecular ion will appear at an even mass value.
• On the other hand, a molecule with an odd number of nitrogen atoms will form a
molecular ion with an odd mass.
▪ The Nitrogen Rule stems from the fact that nitrogen, although it has an
even mass, has an odd-numbered valence.
Stevenson’s Rule
• The most probable fragmentation is the one that leaves the positive charge on the
fragment with the lowest ionization energy.
o In other words, fragmentation processes that lead to the formation of more stable
ions are favoured over processes that lead to less stable ions. (Doesn’t that sound
familiar?)
• When the loss of more than one possible radical is possible, a corollary to Stevenson’s
Rule is that the largest alkyl radical will be lost preferentially.
Common Fragmentation Patterns
• Benzene and alkylbenzenes have mass spectra showing the molecular ion as the base
peak, as the benzyl cation is relatively very stable due to delocalization of the positive
charge throughout the ring.
Column Chromatography
• The stationary phase is held in a narrow tube
through which the mobile phase is forced through
elution or the effect of gravity.
o This is an example of adsorption
chromatography.
• The column is packed with silica gel or alumina
completely saturated with a solvent. The solvent
is clearly the mobile phase while the silica or
alumina is the stationary phase.
• The different components of the sample have
differential affinities for the stationary and
mobile phases.
• On continued elution (addition of solvent/eluent), the
components with higher affinity for the mobile phase
will pass through the column faster.
• What passes through is often called the eluate.
Phase Separations
• Phase separation is simply concerned with methods of separating mixtures into their
constituent components, usually through changes of state (the states of matter are also
referred to as phases).
• Distillation is one form of phase separation, along with solvent extraction.
Distillation
• Distillation is a method of separation of components from a liquid mixture which
depends on the differences in boiling points of the individual components and the
distributions of the components between a liquid and gas phase in the mixture.
o It is split into two types, simple distillation and fractional distillation.
Simple Distillation
• This is used to separate:
o Liquid solutions of substances with widely differing boiling points (>25°C).
o Liquids from involatile solids or oils.
• In the apparatus, vapours rise from the solution in the flask being boiled. In simple
distillation, these are pure vapours since the components being separated have such
different boiling points. They pass into the Liebig condenser, which causes them to
condense and pass along as liquid to the conical flask. This deposited condensed liquid is
called the distillate.
• One component is boiled away while the other remains in the original flask, resulting in
separation.
• It involves a single vaporization/condensation cycle.
Fractional Distillation
• This is used to separate:
o miscible liquids which have close boiling points (<25°C)
o chemically similar components (like ethanol and water)
• It is similar to simple distillation except that a fractionating column is placed between
the flask and the condenser.
o A fractionating column is a vertical tube packed with inert fragments that provide
a large surface area for the vapours rising from the flask to cool, condense and
then vaporise again.
▪ Doesn’t that sound similar to a column in chromatography? The difference
being that chromatography separated based on affinity for the stationary
phase versus the mobile phase, while fractional distillation does so based
on difference in boiling point.
• Fractional distillation involves a series of vaporization/condensation cycles.
o Thanks to the fractionating column, vapour rises up the column then condenses.
When it re-evaporates, it rises further up the column and condenses again.
o With each cycle, the vapour becomes enriched in the component with the lower
boiling point.
o Some condensed liquid which is richer in the less volatile component falls down
the column.
• The motive force for the separation is the drive towards thermodynamic equilibrium
between the different phases.
o This equilibrium is constantly
disturbed by colder descending
liquid and the hotter vapour
rising.
• At equilibrium, a temperature gradient
exists across the length of the column.
• The mode of action of fractional
distillation can be explained with
reference to Raoult’s Law.
Raoult’s Law
• Raoult’s Law states that the vapour pressure of a liquid component of a mixture is equal
to the vapour pressure of the pure liquid at the temperature of the mixture multiplied
by the mole fraction of the liquid present.
o 𝑝𝐴 = 𝑃𝐴0 × 𝑋𝐴
o Vapour pressure is the pressure exerted by the vapour of a liquid in equilibrium
with its liquid phase at a given temperature.
▪ It represents the tendency of a liquid to evaporate, as a higher vapour
pressure corresponds to a lower boiling point, as equilibrium leans
towards evaporation more than condensation. A lower vapour pressure
corresponds to a higher boiling point, as particles of the liquid are less
likely to escape.
o Mole fraction of a particular component of a mixture is the ratio of the number of
moles of that component to the total number of moles in the mixture.
𝑛𝑎
▪ 𝑋𝑎 = 𝑛 +𝑛 for a mixture containing a and b
𝑎 𝑏
• Raoult’s Law however only applies to ideal mixtures.
o An ideal mixture is one where the interactions between molecules of the different
components are the same as those between molecules of the pure substances.
o That is, intermolecular forces between unlike molecules are of equal strength to
those between like molecules.
o A corollary of Raoult’s Law is that for an ideal mixture, the total vapour pressure
of the mixture is equal to the sum of the partial pressures of the components,
𝑝𝑡𝑜𝑡𝑎𝑙 = 𝑝𝐴 + 𝑝𝐵
A graph of Vapour Pressure versus Mole Fraction Composition for an ideal mixture.
• For an ideal mixture, the enthalpy of mixing is zero.
o Enthalpy of mixing is the enthalpy change resulting from mixing two substances
due to the formation of intermolecular forces between unlike molecules and
breakage of intermolecular interactions between like molecules.
o Since the energy of the interactions between like and unlike molecules are equal,
the net change in energy is zero.
• No ideal mixture exists, but some are fairly close:
o Water and methanol
o Propan-1-ol and propan-2-ol
o Butan-1-ol and butan-2-ol
o Hexane and heptane
o Benzene and toluene
Non-Ideal Solutions and Deviations from Raoult’s Law
• The more dissimilar the nature of the components of a mixture, the more the solution is
expected from the ideal.
o No ideal mixture exists, as stated above; as such, vapour composition graphs are
always, in reality, curves.
• Deviations from Raoult’s Law can be categorized as either positive or negative.
The maximum vapour pressure of the curve occurs at a particular composition called a
positive or pressure maximum azeotrope.
The graph is essentially flipped to show boiling point. As the A-B interactions are weaker than
A-A or B-B interactions, molecules escape more easily than expected, i.e. at lower temperatures.
The red curve represents vapour composition while the blue curve represents the composition
of the liquid at that temperature.
That minimum point is called a minimum boiling point azeotrope. The vapour composition is
equal to the liquid composition.
The composition at which minimum vapour pressure is achieved is called the negative
azeotrope or the minimum pressure azeotrope.
That maximum point is called a maximum boiling point azeotrope. The vapour composition is
equal to the liquid composition for a mixture of this composition.
Vacuum Distillation
• This involves carrying out distillation in an environment of reduced pressure (lower
than atmospheric pressure).
o Vacuum distillation is preferred when the compounds being separated are soluble
in water and miscible.
• Boiling occurs when vapor pressure of a liquid or solution equals or exceeds the
external/applied pressure.
o Naturally, if the external pressure is reduced, a lower vapour pressure is required
for boiling, which can be achieved at a lower temperature.
o The boiling point is decreased.
• This is used to separate mixtures of compounds with high boiling points or compounds
that decompose thermally at higher temperatures.
o In the petroleum industry, it is carried out to distil higher boiling point fractions
without causing thermal cracking.
• Advantages:
o Less energy required for heating.
o Thermal decomposition is avoided for certain compounds.
Steam Distillation
• In steam distillation, temperature sensitive
components immiscible with water can be
separated.
• Steam is introduced into the mixture, but as
steam (water) and the mixture are immiscible,
they both exert vapour pressure as if the other
were absent.
• This increases the total vapour pressure of the
system.
• Since boiling occurs when the vapour pressure of a liquid just exceeds the
ambient/external pressure, the increase in vapour pressure will decrease the boiling
point, allowing distillation to occur at a lower temperature, which is perfect for
compounds that decompose near their boiling points.
• This method is used in separating:
o Eugenol from cloves
o Eucalyptus oil from eucalyptus
o Citrus oils from lemon/orange peel
• In steam distillation, the ratio of the moles of the two compounds in the distillate is equal
to the ratio of their vapour pressures:
𝑛 𝑝
o 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 = 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
𝑛
𝑤𝑎𝑡𝑒𝑟 𝑝𝑤𝑎𝑡𝑒𝑟
Solvent Extraction
• Also called liquid-liquid extraction, this is a technique in which a solution (usually
aqueous) is brought into contact with a second (usually organic) solvent immiscible with
the first, in order to bring about transfer of one or more solutes into the second solvent
based on differential solubility of the desired solute in either immiscible solvent.
• When a solute is shaken with a pair of immiscible liquids, it partitions between the two
liquids based on the partition law, or Nernst’s Distribution Law.
o This law states that, provided that its molecular state is the same in both liquids,
both solutions are dilute and that the temperature is constant, the ratio between
the concentrations of the solute in both solvents will be constant at equilibrium.
o 𝑋𝑎𝑞𝑢𝑒𝑜𝑢𝑠 ⇌ 𝑋𝑜𝑟𝑔𝑎𝑛𝑖𝑐 represents the equilibrium that exists.
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑙𝑎𝑦𝑒𝑟
o 𝑘𝑝𝑐 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑞𝑎𝑢𝑒𝑜𝑢𝑠 𝑙𝑎𝑦𝑒𝑟
o Where 𝑘𝑝𝑐 is the partition coefficient, an equilibrium constant for this system.
• Solvent extraction is more efficient when a certain volume of the extracting solvent is
used in small successive portions rather than all at once.
Procedure
1. The organic compound/product in aqueous solution is shaken up with a small quantity of
organic solvent in a separatory funnel.
a. The tap is opened periodically during the shaking to release pressure caused by
the evaporation of solvent vapours.
b. Any solid impurities are filtered off.
2. The mixture is left to stand, allowing separation of the liquids into two distinct layers,
each of which can be drained separately through the tap. The organic layer, which
contains the organic product dissolved in the organic solvent, is kept and referred to as
the extract.
3. Since trace amounts of the desired organic product still remain in the aqueous layer, the
shaking and separation procedure is repeated at least twice, each time using fresh
solvent. All the product extracts are combined.
a. Recall that solvent extraction is more efficient if the solvent is used in successive
small portions rather than all at once.
4. The organic solvent may then be distilled off, leaving the pure solid.
Locating Industrial Plants
Factors Influencing Location of an Industrial Plant
• Suitability of terrain
• Vulnerability of an area to weather/natural disaster events
• Availability and Proximity of building materials
• Availability of safe disposal systems
• Availability of commodities like water
• Access to sufficient electrical power
• Proximity of skilled workers
• Effect on nearby community- providing employment versus using up productive
farmland.
Health and Safety
• Choosing processes and tools which are inherently safe
• Identifying hazards which cannot be eliminated, and instituting training on how to cope
with it
• Having plans for coping with large-scale emergencies like hurricanes and ensuring staff
has had chance for training and practice
• Ensuring that emergency exits are clearly marked
• Training staff in proper procedures including use of personal protective equipment (PPE)
• Having some staff qualified in first aid
Aluminium
Ore Purification
• Purification of aluminium ore occurs via the Bayer process.
• The constituent of interest of aluminium ore (bauxite) is aluminium oxide, and
amphoteric compound.
o The main impurities of bauxite are iron (III) oxide, silicon dioxide and titanium
oxide.
o Fe2O3 is basic while SiO2 is acidic.
STEP ONE (Digestion)
• Ground bauxite is mixed with hot sodium hydroxide solution in a process called
digestion.
o Amphoteric aluminium oxide reacts with the caustic soda to form soluble sodium
aluminate
▪ Al2O3(s) + 2NaOH(aq) → 2NaAlO2(aq) + H2O(l)
▪ Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)
o Acidic silicon dioxide reacts with the caustic soda to form soluble sodium silicate
▪ SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
o Basic iron oxide remains unreacted and undissolved
STEP TWO (Filtration)
• The insoluble impurities like the iron oxide are filtered out as red mud, and only the
soluble products move on.
STEP THREE (Precipitation)
• The heated filtrate is stirred and cooled, causing the precipitation of aluminium
hydroxide crystals.
o NaAlO2(aq) + 2H2O(l) → NaOH(aq) + Al(OH)3(s)
o A crystal of aluminium hydroxide is usually used to seed the mixture and
jumpstart precipitation.
• Carbon dioxide is also pumped through the solution to trigger precipitation.
o 2[Al(OH)4]-(aq) + CO2(g) → 2Al(OH)3(s) + CO32-(aq) + H2O(l)
STEP FOUR (Filtration)
• The silicates remain in solution, leaving aluminium hydroxide (hydrargillite) crystals.
STEP FIVE (Calcination)
• The filter residue is heated in a rotary kiln at 1100 to 1300 degrees Celsius, which drives
off water, leaving near pure aluminium oxide (alumina).
o 2Al(OH)3(s) → Al2O3(s) + 3H2O(l)
Production
• This occurs through the Hall-Heroult Process.
o This process is essentially hydrolysis of the molten alumina.
o Alumina melts at 2050 degrees Celsius, which is very high and requires a lot of
power.
o This melting point can be decreased to around 960 degrees Celsius by dissolving
alumina in molten cryolite
(NaAlF6) and fluorspar (CaF2).
This also increases conductivity.
• The aluminium oxide is thought to
dissociate into aluminium ions and oxide
ions in solution.
• At the cathode (carbon lining), the half
equation is: O2-(l) + C(s) → CO(g) + 2e-
• At the anode (carbon rods), the half equation is: Al3+(l) + 3e- → Al(l)
• The molten aluminium can then be let off through the outlet.
Aluminium Uses
• Physical properties include:
o Lustrous, silvery white colour
o Lightweight
o Relatively soft and malleable
o Low density
o High thermal and electrical conductivity
o Highly reflective when polished
• Chemical properties include:
o Natural formation of a thin coating of aluminium oxide on the surface on
exposure to air, which protects it from further oxidation (resistant to corrosion).
o Easily recyclable (100%)
Property Usage
Non-toxic Used for cans and food-grade packaging
Resistant to corrosion Used in window frames and kitchen utensils
Highly reflective under certain conditions Used in telescope mirrors and firefighter
garments
Thermally conductive Pots and pans
Lightweight Alloyed with Copper, manganese, magnesium
or silicon for use in the bodies of aircrafts and
spacecrafts
Crude Oil
Separation Method
• The separation of crude oil occurs through fractional distillation.
• Hydrocarbons, mainly alkanes, are the main and most important components of crude
oil. Longer chain hydrocarbons have higher boiling points than shorter chain
hydrocarbons.
o Since crude oil contains alkanes with chain lengths from 1 carbon to over 70, the
components can be separated based on their differences in boiling points.
• Industrial fractional distillation of
crude oil involves heating the oil at
the base of the fractionating column
to 300°C.
• The liquid that doesn’t boil is
simply piped off as residues. This
is the heaviest fraction.
• The rest of the liquid, which boils,
rises as vapours through the
fractionating column, across which
there is a temperature gradient- the
top being the coolest.
• A hydrocarbon compound will
condense when it reaches a part of
the column that is below its boiling
point, where is will be collected and
piped off.
• The vapours which don’t condense
are piped off at the top as refinery
gases. This is the lightest fraction.
The Fractions of Crude Oil and their Uses
Carbon Chain
Fraction Boiling Range Uses
Length
Refinery Gases <5°C C1 to C4 LPG for cooking
High octane gasoline,
Naphtha 20-180°C C5 to C9
diluting bitumen
Fuel for motor
Gasoline (Petrol) 40-200°C C5 to C10
vehicles
Fuel for jet engines,
Kerosene (Paraffin
150-260°C C10 to C16 kerosene lamps
Oil)
(domestic heating)
Fuel for diesel
Diesel (Gas Oil) 260-340°C C14 to C20 engines (cars and
large vehicles)
Lubrication, wax,
polishes, candles,
Lubricating Oil >370°C C20 to C50
solvent for petroleum
jelly
Paraffin Wax >C40 Insulation
Road surfacing,
Bitumen/Tar/Asphalt >C70 waterproofing and
sealing
Reforming
• Reforming is a process in which straight-chain hydrocarbons (with a low octane rating)
are broken up and then reassembled into aromatic and branched-chain hydrocarbons
(with a high octane rating).
• These ‘higher octane ratings’ (meaning more highly branched compounds) are more
resistant to knocking, or the premature combustion of fuels in an engine implicated in
engine damage and overheating.
Environmental Impact
• All stages of the crude oil industry- exploration, extraction , transportation, refining and
use- are major sources of pollution.
• Exploration, or the search for crude oil, has significant impact on the environment.
o Seismic surveys are used to determine underground oil deposits. These surveys
require shock waves which are usually generated using explosions in the ocean or
underground.
▪ This destroys ecosystems and wildlife.
o Exploratory wells are drilled at prospective oil sites. If no oil is found, they can
sometimes be left abandoned.
• Extraction is the procurement of oil from the oil deposit discovered in the well.
o The surrounding land is cleared and levelled, which destroys flora, fauna and
habitats.
o If no water is nearby, large water wells are drilled, which is highly damaging.
o Well drilling expels both brine and oil into surrounding soil and water, which
damages plant life and aquatic life.
• Transportation is also a potential environmental hazard.
o Oil tanker spills kill marine life and contribute to reduce air quality if they catch
ablaze.
▪ Birds can also be affected if the oil reaches their feathers.
▪ Coral reefs are killed due to blockage of sunlight.
▪ Polar bears freeze to death when they lose insulation due to their fur
being stuck down by oil.
o April 20th 2010, an explosion on the Deepwater Horizon drilling rig killed 11 of
the 126 crew members and spilled about 4.9 million barrels of oil into the Gulf of
Mexico.
• Refinery process releases toxic and hazardous air pollutants (many of which are
greenhouse gases).
o Carbon monoxide
o Nitrogen Oxides
o Benzene, toluene, ethylbenzene and xylene (BTEX compounds)
• Use of petroleum fractions as fuels releases compounds like carbon dioxide and
nitrogen oxides into the environment.
Ammonia
Production/Haber Process
• The Haber Process can be simplified as a reaction combining hydrogen and nitrogen to
form ammonia:
o N2(g) + 3H2(g) → 2NH3(g), Δ𝐻 = −92 𝑘𝐽𝑚𝑜𝑙 −1 (exothermic reaction)
• Hydrogen gas is obtained via steam reforming, that is, reacting methane with steam
o CH4(g) + H2O(g) → CO(g) + 3H2(g)
o Nickel catalyst at 700-1100°C and 20 atm.
• Additional hydrogen is recovered from the steam through the water gas shift reaction.
o CO(g) + H2O(g) → CO2(g) + H2(g)
o Nickel oxide catalyst at 130°C.
• Nitrogen gas is procured from the fractional distillation of liquified air.
• The purified nitrogen and hydrogen gases are the mixed and compressed to 150-250 atm
and passed over an iron catalyst at temperatures around 400°C.
o This combination produces a 10% yield of ammonia.
• The equilibrium gas mixture leaves the reactor, where it is then cooled.
o Ammonia condenses (as it has a much higher boiling point), but the nitrogen and
hydrogen remain gaseous, and can be recycled into the reactor while the
ammonia is piped off.
o Thanks to the recycling of gases, a ~97% yield can be obtained by maintaining
the position of the equilibrium to the right.
Explaining the Equilibrium Conditions
• N2(g) + 3H2(g) → 2NH3(g)
• The equilibrium needs to be shifted to the right to increase the yield.
• Le Chatelier’s principle (which states that if dynamic equilibrium is disturbed by a
change in conditions, the position of the equilibrium will shift to oppose the change in
conditions) allows us to determine the conditions necessary to produce the highest
theoretical yield.
o 4 moles of reactants gives 2 moles of reactants, so high pressures will shift the
equilibrium to the right. This is why high pressures are used in the Haber process.
▪ Though this is limited because high pressures are expensive to maintain,
and requires costly, high maintenance equipment.
o The reaction is exothermic (releases heat), and as such, lower temperatures will
shift the equilibrium to the right. However, low temperatures also slow the rate of
reaction.
▪ The reaction must proceed at a viable rate, and so, temperatures are kept
moderately high.
Uses of Ammonia
• Agriculture: Production of nitrogen fertilizers (usually as ammonium
nitrate/sulphate/phosphate by reaction with acids), which provide nitrogen in soluble
form to support plant growth.
• Chemical Industry: manufacture of nitric acid, plastics, pharmaceuticals, commercial
and household cleaners (like glass cleaner!)
• Ammonia is also used in the food and beverage industry as a nitrogen source for yeast
• Used as a refrigerant gas
Impact of Ammonia Industry on the Environment
• Carbon dioxide from the steam-reforming process is emitted, however it is often used in
urea production.
• The catalysts used in ammonia production need to be replaced every 2-6 years, which
can be an issue if not properly recycled.
• The use of ammonia in agriculture can be an environmental hazard:
o Excess fertilizers entering natural waters results in eutrophication. This ends in
death of aquatic organisms.
o Fertilizer runoff can enter domestic water supply, polluting drinking water.
Nitrates of fertilizers are poisonous, especially to babies.
o Soil acidification results when ammonium ions in the soil are nitrified by
bacteria, releasing hydrogen ions. This acidity can af6fect plant growth.
o Smog particles are formed when ammonia combines with nitrogen oxides and
sulphur dioxides in the atmosphere
Ethanol
Production of ethanol occurs by fermentation of sugars, followed by distillation to increase the
concentration of ethanol produced.
Production/Fermentation
• Fermentation is the process by which sugars are oxidized by living organisms in the
absence of oxygen to release energy.
o Yeast (Saccharomyces cerevisiae) is a unicellular fungus which releases ethanol
and carbon dioxide as products of anaerobic respiration.
• Yeast is combined with a solution containing sugars and a nitrogen source (like
ammonia). The solution is kept in a fermenter under anaerobic conditions (oxygen
absent).
o The temperature is kept at a fairly low 25°C, as temperatures too high or low
adversely affect the activity of enzymes in the yeast.
o When ethanol concentration reaches 12-15% however, the activity of the yeast
stops as the enzymes are denatured by the toxic ethanol.
• To increase the concentration of alcohol in the solution to the wonderfully deleterious
levels found in spirits (even up to 40% alcohol by volume), fractional distillation must
be carried out.
Fractional Distillation
• We already discussed fractional distillation in a previous section.
• Ethanol is being separated from a mixture with water.
o Since these two compounds have boiling points within 25 degrees Celsius of each
other (water 100°C versus ethanol at 78.5°C), fractional distillation must be used.
• The mixture of ethanol and water has a minimum boiling point azeotrope (78.2°C) at
95.6% ethanol and 4.4% water however, meaning that the maximum concentration of
ethanol that can be procured from the 15% ethanol solution is 95.6% ABV.
• Absolute, or pure ethanol can be procured from the azeotropic mixture by combining
the azeotrope with an additional agent (called an entrainer) like cyclohexane.
o The resulting ternary azeotrope can be distilled to attain the pure ethanol.
Uses of Ethanol
Fuels
• Ethanol has a very clean (non-smoky) and exothermic combustion. As such, it is used as
a fuel additive.
o For example, E85 is a mixture of 85% ethanol and 15% gasoline commonly used
in many vehicles and gas-powered equipment.
Alcoholic Beverages
• This is the most familiar use of ethanol. Alcoholic beverages are the most commonly
consumed drugs.
Solvents
• Ethanol is used as a solvent for dissolving many organic compounds, including
pharmaceuticals, cosmetics, perfumes and paints
• It is also used as a disinfectant for wounds thanks to its antiseptic properties.
Solvents
• Chlorine is a substituent in common organic solvents like tetrachloromethane (now
phased out due to environmental risk) and chloroform.
Anaesthetics
• Halothane (2-bromo-2-chloro-1,1,1-trifluoroethane) is a commonly used inhalational
anaesthetic.
Sulphuric Acid
Production
• Production of sulphuric acid occurs through the Contact Process.
• It has four main stages:
o Production of sulphur dioxide
o Oxidation of sulphur dioxide to sulphur trioxide
o Hydration of sulphur trioxide to oleum
o Dilution of oleum to concentrated sulphuric acid
The above has some intermediary cleaning and drying steps that weren’t fully explained, but the
principle is the same.
Water
Importance of the Water Cycle
• The water cycle or hydrological cycle is the cyclical process of evaporation and
condensation of water on the surface of the Earth.
• The water cycle is a self-purifying system that helps to maintain ecological balances.
Water is necessary for
o Drinking
o Domestic purposes
o Photosynthesis
o Digestion
o Excretion
o Agricultural Use
o Solvent Use
o Industrial Use
o Electricity Generation
Methods of Water Purification
• Filtration is a very common method of water purification utilized in household and
small-scale settings. It involves mechanical separation of solids from water.
o Screen filters are made of metal, plastic or fibre to remove large debris.
o Carbon filters are made of pieces of charcoal activated with a positive charge,
allowing the removal of sediments, organic compounds and chlorine.
o Sand filters- made of layers of sand or other particulate materials.
o Membrane filtration- semi-permeable membrane coupled with high pressures,
which removes microscopic organisms and particles.
• Desalination- the removal of salts from sweater to produce fresh water for other use.
o Flash distillation
o Electrodialysis
o Ion exchange
o Reverse Osmosis
o Freeze Desalination
• Chemical Treatment
o Step 1: Clarification
▪ Coagulant (like aluminium sulphate) added to the water which causes
particulate contaminants to flocculate into larger particles which can be
easily filtered.
o Step 2: Disinfection
▪ Water is treated with chlorine or another disinfectant like bleach or ozone.
▪ This does not work against certain chlorine-resistant protozoans like
Giardia or Cryptosporidium, and the chlorine may form carcinogenic
compounds with organic materials in the water.
▪ Residual disinfectant may also remain in the water.
• UV Radiation
o UV radiation acts as a mutagen which is able to irreversibly damage the DNA of
organisms, rendering them incapable of causing harm.
Importance of Dissolved Oxygen to Aquatic Life
• Aquatic life relies on dissolved oxygen (DO) in the water for respiration, a process
essential for the continuation of life.
o Without adequate dissolved oxygen, aquatic animals will die as they will be
unable to carry out aerobic respiration.
• Oxygen gets into rivers, lakes and the sea through:
o Diffusion through the water surface from the air
o Diffusion from bubbles of trapped air or from photosynthesis of aquatic plants.
o Process of photosynthesis
• The amount of DO in water depends on several factors:
o Temperature and pressure- higher temperature and lower pressure decrease
DO.
o Salinity- Saltwater has a lower DO content than freshwater.
o Stagnation- Stagnant water has less DO than flowing water.
o Bacterial content- these organisms remove oxygen from water.
• At DO levels of 3-5 ppm (parts per million), aquatic life is put under stress, and below 2
ppm, organisms start to die.
Sources of Water Pollution
• Water pollution is the discharge of pollutants and contaminants into bodies of water
without suitable treatment to remove unsafe compounds.
Pollutant Source
Nitrates Leaching of fertilizers
Leaching of fertilizers and phosphates from
Phosphates
detergents
Mercury from the chlor-alkali industry and
dumping of fluorescent bulbs
Heavy Metals
Lead from old water pipes and petrol
Cadmium from batteries
From metal extraction industries (silver, gold,
Cyanides
iron, steel)
Aluminium from clay extraction, trace
Other Metals
elements leaching through soil, nuclear waste
Pesticides and herbicides (like DDT) Washing from crop fields into water bodies
Petroleum residues Oil spills
Particles of clay and other materials washed
Suspended particles
from quarries, construction sites and homes
Add iron (II) sulphate to the solution then A deep blue coloration
Cyanide
acidify with hydrochloric acid. (complex ion) is formed.
The Atmosphere
The atmosphere is the blanket of air surrounding Earth held in place by the force of gravity.
o ClO then reacts with ozone once more to form oxygen and reproduce the
chlorine radical. Chlorine acts as a catalyst as it is regenerated.
o ClO may also simply react with an oxygen radical to form the chlorine radical
and oxygen:
• Each chlorine radical (from a single CFC molecule) can catalyse the breakdown of about
100000 ozone molecules before a termination reaction occurs (simply a reaction
between two radicals).
Effects of Ozone on Human Life
Ozone in the Stratosphere
• The reactions involving the photo-activated formation and destruction of ozone rely on
absorption of light in the UV range of the sun’s radiation, and as such, absorbs
significant amounts of potentially harmful UV light.
o Recall that UV light, in excessive dosages, can damage the genetic material of
organisms.
o Increased UV exposure is linked to higher incidence rates of skin cancer and
cataracts in humans
• Ozone helps to exclude UV radiation. However, absorption of UV radiation from the sun
by the skin is necessary for about 90% of the Vitamin D production of the human body
Releasing CO2 into the Atmosphere Uptake of CO2 from the Atmosphere
Photosynthesis/Carbon fixation by plants and
Respiration (CO2 is a waste gas)
some bacteria.
Fuel Combustion (combustion reactions
release CO2 and H2O when complete)
Decomposition of organic matter
Release of CO2 from oceans (especially upon
Dissolution of CO2 in oceans (the reverse
warming)
reaction on the left)
2HCO3-(aq) ⇌ CO2(g) + H2O(l) + CO32-(aq)
Volcanic activity
As can be seen in the carbon cycle above, removal and adding of CO2 to the atmosphere occurs
in a cyclical nature.
Photosynthesis and respiration are balanced and the uptake and release of CO2 from oceans
is also balanced. If this balance is not disrupted, the level of CO2 in the atmosphere can remain
constant.
• Deforestation and combustion of fossil fuels are putting the carbon cycle out of balance.
o Deforestation reduces the global rate of photosynthesis by eliminating plants,
which is one of the only ways carbon is taken up from the atmosphere.
o Fossil fuel combustion causes the release of carbon dioxide.
o Global warming increases the temperature of oceans and shifts the equilibrium
of bicarbonate dissociation and formation in the direction of dissociation and
release of CO2.
• Reforestation efforts are necessary to restore the balance between photosynthesis and
respiration.
Some Definitions
Greenhouse Effect
• This is the phenomenon wherein radiation from the sun reflected from the earth as
longer-wave infrared is absorbed by certain greenhouse gases in the atmosphere which
re-radiate this energy back to earth’s surface (rather than allowing it to pass into space) to
contribute to warming of the earth.
Global Warming
• Global warming is the gradual increase in the temperature of earth’s surface as
contributed to by the greenhouse effect.
• Global warming is actually a major contributor to habitable conditions on earth, as
without it, the surface would be too cold for life to exist. It is the enhanced global
warming due to the emission of many greenhouse gases into the atmosphere (CO2, CH4,
CFCs, water vapour) which causes today’s concerns.
Photochemical Smog
• This is a mixture of pollutants (seen as a brown haze) that are formed when nitrogen
oxides and volatile organic compounds (VOCs) react in the presence of sunlight.
• Recall from above:
Acid Rain
• Acid rain describes rain with a pH below 5, formed from the reaction between oxides of
sulphur and nitrogen in the atmosphere reacting with water vapour.
• Sulphur dioxides come from the burning of impure fuels containing sulphur, as well as
from volcanic eruptions.
Formation of Acid Rain
The formation of acid rain occurs in two stages, oxidation and deposition.
Oxidation
• This involves the oxidation of SO2 and NO2 to form acidic gases SO3 and NO2.
• Oxidation of SO2 can be catalysed by NO2 or by free radicals
o SO2(g) + NO2(g) → SO3(g) + NO(g)
▪ This reaction is followed by the regeneration of NO2:
2NO(g) + O2(g) → 2NO2(g)
o Oxidation with oxygen free radicals or ozone:
SO2(g) + O3(g) → SO3(g) + O2(g)
o Oxidation to sulphates by OH• (formed by the action of oxygen radicals with
water)
OH•(g) + SO2(g) → HSO3•(g), which is then oxidized to sulphuric acid.
• Nitric Oxide can also react with oxygen radicals or ozone to form acidic NO2 gas
o NO(g) + O•(g) → NO2(g)
Acid Formation/Deposition
• This is simply how the acids form through reaction with water.
• Deposition can occur as dry deposition or wet deposition.
• Wet deposition- NO2 and SO3 react with water vapour in the atmosphere to form dilute
solutions of nitric, nitrous and sulphuric acid, which fall with the rain as acid rain.
o SO3(g) + H2O(l) → H2SO4(aq)
o 2NO2(g) + H2O(l) → HNO3(aq) + HNO2(aq)
• Dry deposition- small particles of sulphates and nitrates can form in the atmosphere
when the acids react with ammonia in the atmosphere.
o These compounds and dry SO2 and SO3 gases can then react with water on moist
surfaces like wet buildings to form acids.
Methods of Control and Prevention of Atmospheric Pollution
Prevention
Alternative and Cleaner Fuels
• Biofuels are common alternative fuels which do not disrupt the carbon cycle. The waste
products from the production of biofuels (plants) can be reduced, reused and recycled.
o Examples of biofuels include biodiesel, ethanol, gasohol and biogas
• Fuel cells are electrochemical cells which convert some form of chemical fuel (like
hydrogen) into electrical energy.
o They only produce heat and water as waste products, making them essentially
zero emission fuel sources
o The hydrogen they require must be acquired through production like steam
reforming and electrolysis, which are both energy consuming.
Particular Technology
• Catalytic converters use platinum-rhodium catalysts to convert nitrogen oxides and
carbon monoxide to harmless nitrogen gas and non-toxic carbon dioxide.
Mass Transit
• When transportation is done en masse using public transportation, it reduces the need for
individual automobiles.
o This reduces air pollution and emissions from individual vehicles.
Control
Sequestering
• In sequestering, greenhouse gases like carbon dioxide are trapped by reaction with
substances like metallic oxides to form stable compounds like carbonates.
Filters
• Small particulate matter (like dust and smoke) are removed using filters like air filters
and electrostatic precipitators.
Washers
• Washers dissolve pollutants in a solvent to remove them from air exhaust.
Scrubbers
• Scrubbing makes use of alkalis or basic compounds to neutralize acidic gases in the
atmosphere.
• An example of this is flue-gas desulphurisation.
Solid Waste
Reduce, Reuse, Recycle
• Reducing/Waste reduction is the prevention of the creation of waste material.
• Reuse is simply using a material or item more than once.
• Recycling involves processing used materials into fresh products.
Waste Reduction
• Investing in more durable products
• Limiting the use of disposable products
• Repairing broken items instead of purchasing replacements
• Manufacturers can use minimal packaging
• Manufacturers can utilize all components of a raw material to reduce waste
Glass
• Waste glass can be sorted and melted to make new objects or added to freshly made
glass.
• Recycled glass can be used:
o To make new glass bottles
o To be included in concrete or ceramic
o As an abrasive in glasspaper
Paper
• Paper undergoes a process of sorting and grading, then pulping, then screening, de-inking
and refining and bleaching. After this, the recycled paper pulp can be converted into
sheets.
• While glass is infinitely recyclable, paper can only be recycles about 5-7 times as the
fibers will shorten and weaken.
Plastic
• Thermoplastics, or those that melt when heated, make up most of recycled plastic.
Steel
• Scrap iron or steel is simply melted and added to a furnace. This reduces carbon
emissions by about 60% when compared to newly produced iron.
Aluminium
• The aluminium is melted and added to a furnace then degassed to remove hydrogen. It is
then recast. Recycling aluminium reduces carbon emissions by 95% and energy
consumption by 95% compared with making aluminium from bauxite ore.
Disposal Methods
• Dumping: This is very common due to its ease, throwing garbage into streets, roadways
and gullies.
• Landfill: Waste can be buried in a landfill site, like an unused quarry or mine.
o Landfills can either be waste dumps or sanitary landfills
• Composting is allowing the natural breakdown of organic plant and animal material in
aerobic conditions
• Nuclear waste disposal can be achieved safely through:
o Vitrification: mixing with molten glass
o Adsorption: Addition to an ion-exchange resin which is then mixed with cement.
o Above ground disposal: The waste is placed into a steel cylinder, and an inert
gas is then added.