Module 8 Summary Notes

IQ1: Analysis of Inorganic Substances

Inquiry Question: How are the ions present in the environment identified and
measured

The Need for Monitoring the Environment

Syllabus Dot Point: Analyse the need for monitoring the environment

• It is necessary that humans prevent the presence of harmful chemicals in the

environment
• To achieve this, the careful monitoring of the environment is required

Air Pollution
Pollutant Source Effect
Sulfur - Combustion Can react with water to form acid rain
Dioxide - Metal extraction - Destroys limestone and organic building
- Chemical material
manufacturing
This is an undesirable outcome as as it costs
money to replenish and repair the damages
CFC’s Pre- 1996 - Destroys the Earth’s protective Ozone layer
- Refrigeration allowing for UV rays to enter the
- Air-conditioning atmosphere
- Plastics - Contributes to the warming the
temperatures of the Earth

This is an undesirable outcome as contributes to

climate change which disrupts the liveability for
humans and other important ecosystems

Water Pollution
Pollutant Source Effect
High Suspended soils and High turbidity reduces the water’s ability to
Turbidity particles in the water. support marine lives.
These stem from:
- Land clearing
- Farming
High Fertiliser run-off from Encourages algal blooms
[NO3-], Agriculture
[PO43-]

Soil Pollution
Source Effect

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 Chemical Spills, Improper Plants grown in polluted soil will absorb these pollutant
Disposal of Toxic Chemicals molecules. The consumption of these polluted plants can
+ Polluted Rain cause
- Developmental damage in children
- Kidney and liver damage for humans due to excessive
mercury in soil
- Influence of developing cancer due to carcinogenic
molecules in plants

Qualitative Investigations of Inorganic Compounds

Syllabus Dot Point: Conduct qualitative investigations – using flame tests, precipitation and
complexation reactions to test for the presence in aqueous solution of the following ions:
- Cations: (Ba2+), calcium (Ca2+), magnesium (Mg2+), lead(II) (Pb2+), silver ion (Ag+),
copper(II) (Cu2+), iron(II) (Fe2+), iron(III) (Fe3+)
- Anions: chloride (Cl–), bromide (Br–), iodide (I–), hydroxide (OH–), acetate
(CH3COO–), carbonate (CO32-), sulfate (SO42-), phosphate (PO43-)

Flame Tests
• When metals are heated, the electrons temporarily move up in orbital due to the
additional energy, when they go back their initial orbital, energy is released in the form of
light
• Flame tests cannot confirm the presence of anions, only metal cations
• Flame tests cannot be used to identify solutions containing more than one type of
distinctive metal

Element Flame Colour

Lithium Carmine (dull red)
Sodium Yellow
Potassium Light-purple (lilac)
Calcium Brick-red (orange-red)
Strontium Scarlet (deep red)
Barium Pale Green (apple-red)
Copper Blue-green

• Metallic ions such as Iron and Silver are colourless since their photon wavelengths are
not within the visible range

Precipitation Tests

Cation:
1. Addition of HCl (Cl- ion) targets Pb2+, Ag+
- If a white precipitate forms, these ions are present
- Add HI (I- ion)to a new sample of solution yellow precipitate formed = presence of
Pb2+
- Add the white precipitate to Ammonia precipitate dissolves = presence of Ag+ (forms
2+
[Ag(NH3)] complex ions)

2. Addition of H2SO4 (SO42- ion) Targets Ba2+, Ca2+

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 - If a white precipitate forms, the ions are present
- Spray a new solution in the flame brick-red flame = presence of Ca2+
- Pale green flame = presence of Ba2+

3. Addition of NaOH targets Cu2+, Fe2+, Fe3+, Mg2+

- If a precipitate forms, these ions are present
- Spray the solution into a flame blue-green flame = presence of Cu2+
- Add acidified potassium permanganate solution decolourises = presence of Fe2+
- Add thiocyanate solution to a new solution forms a blood red solution = presence of
Fe3+
- Add excess ammonia solution to white precipitate if it is insoluble = presence of Mg2+

Anion:
1. pH meter targets OH- , CO32-
- a high pH indicates presence of hydroxide, [OH -] can also be calculated through the pH
- if pH from 8-11 is depicted, add dilute HNO3 bubbles of colourless gas formed (CO 2)
= presence of CO32-

2. Add AgNO3 targets, Cl-, Br-, I-

- If a precipitate forms, these ions are present
- Add dilute ammonia solution to precipitate precipitate dissolves = Cl- is present
- If insoluble, add aqueous Cl2 with organic solvent and shake purple colour is formed
= I- present
- Yellow/Orange colour formed = Br- is present

3. Detecting CH3COO-
- Add dilute HNO3 smell of vinegar + turns blue litmus red = presence of CH 3COO-

4. Detecting SO42-
- Acidify the solution and add Ba(NO3)2 thick white precipitate forms = presence of
ion

5. Detecting PO43-
- Add ammonia followed by Ba(NO3)2 white precipitate forms = presence of ion

Complex ions and Complexation reactions

• A complex ion has a metal ion at its centre with several other molecules or ions
surrounding it
• The surrounding molecules/ions are attached to the central ion via coordinate covalent
bonds
• The surrounding molecules/ions are called ligands

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Note: The arrows depict coordinate covalent bonds

• For the central ion to be surrounded by ligands the ligand must have at least 1 lone
pair or valence electron
• The coordinate number is determined through the number of ligands

Detecting ions using complexation reactions:

• Complexation reactions are in equilibrium
e.g. Co2+(aq) + 6NH3(aq) [Co(NH3)6]2+(aq)

• When transition metal ions dissolve in water, metal complexes form between the ion and
the water molecules
• When other ligands are added to the solution, a ligand exchange reaction occurs
e.g. [Cu(H2O)6]2+(aq) + 4Cl-(aq) [CuCl4]2-(aq) + 6H2O(l)

Due to the presence of a metal ion, each complex has a characteristic colour

Quantitative Analysis of Inorganic Compounds

Syllabus Dot Point: conduct investigations and/or process data involving:
- Gravimetric analysis
- Precipitation titrations

Gravimetric Analysis
• a quantitative method for accurately determining the amount of a substance by selective
precipitation of the substance from an aqueous solution

Principles of Gravimetric Analysis

- ions in an aqueous solution are selectively precipitated
- the precipitate is separated from the remaining aqueous solution by filtration and is
weighed
- With known chemical formula for the precipitate low solubility, the mass of the
substance in the original substance can be determined

Example:
Aim – to determine the mass of SO42- in a 0.5g fertiliser sample

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 1. Dissolve the fertiliser in distilled water
2. Add excess BaCl2 to the solution
BaCl2(aq) + SO42-(aq) BaSO4(s) + 2Cl-(aq)
3. Filter off, dry and weigh the precipitate (m(ppt) = 0.2g)
4. Determine the number of moles for BaSO4
n(BaSO4) = n(SO42-)
5. Determine the mass of sulfate

Maximising Validity in Gravimetric Analysis

• Use excess solution to ensure that all the target ion is precipitated
• Maximise the size of precipitate crystals to prevent loss of ppt during filtration this is
done by decreasing the rate of reaction through the slow addition of the solution
• Minimise impurities adsorbed onto the precipitate crystals this is done through the
maximisation of crystal size

Precipitation Titrations
Terminology:
Analyte: Solution of unknown concentration but known volume
Titrant: Solution of known concentration and known volume
End point: when the indicator undergoes a permanent colour change

Example: Titration of Cl- solution with AgNO3

1. Add a chromate solution to the conical flask
2. Start adding AgNO3, As AgNO3 is added: Ag+(aq) + Cl-(aq) AgCl(s)
3. Eventually, n(Ag+) = n(Cl-) equivalence point
4. The next drop of AgNO3 won’t precipitate with Cl-, instead it will precipitate with
chromate forming a reddish-brown precipitate, this indicates end point
2Ag+(aq) + CrO4- Ag2CrO4(s)

To compensate for the delay between end point and equivalence point, make analyte solution
slightly basic

CrO42-(aq) + H2O(l) OH-(aq) + HCrO4-(aq)

- Making the analyte solution slightly basic shifts the equilibrium to the left

2Ag+(aq) + CrO42-(aq) Ag2CrO4(s)

- Making the analyte solution basic increases the concentration of chromate, this shifts the
equilibrium to the right this bridges the delay between end point and equivalence
point

Choosing the appropriate indicator:

Indicator Colour Change (Ag+ limiting Use
to excess Ag+)
Potassium Lemon-yellow to reddish - Ag+(aq) + Cl-(aq) AgCl(s)
Chromate brown - Ag+(aq) + Cl-(aq) AgBr(s)
(K2CrO4)
Flourescein Green to red - Ag+(aq) + Cl-(aq) AgCl(s)

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 Eosin Green to magenta - Ag+(aq) + Br-(aq) AgBr(s)
- Ag+(aq) + I-(aq) AgI(s)

Determining the concentration of coloured species or metal ions in aqueous solution

Syllabus Dot Point: conduct investigations and/or process data to determine the concentration
of coloured species and/or metal ions in aqueous solution, including but not limited to, the use
of:
- Colourimetry
- Ultraviolet-visible spectrophotometry
- Atomic Absorption Spectroscopy

Atomic Absorption Spectroscopy (AAS):

Emission Spectra
- Electrons in an atom exist in discrete energy levels
- If we heat electrons to a high temperature, some of the electrons get excited and move
from their normal energy levels to a higher energy level
- However, after a short time, these electrons fall back into their normal energy levels,
releasing energy in the form of light
- The energy absorbed from an electron moving up an energy state is the same amount of
energy released when it falls back to its ground state
- An emission spectrum of an element is the spectrum of frequencies of radiation emitted
due to the electron falling back to its ground state
- Each element has a unique electron configuration meaning they have a unique energy
difference between energy states each element has a unique emission spectra
- To excite electrons, atoms can absorb wavelengths of their emission spectra only

Principles of AAS
- AAS uses emission spectra to measure the concentration of particular ions in a solution
- By measuring the fraction of light that is absorbed by an element at a particular
wavelength, it can determine its concentration

Structure and Operation:

1. Hollow Cathode Lamp

- The cathode is made from the element being analysed
- The lamp emits light only from the wavelength of the atom’s emission spectrum

2. Flame
- An aqueous solution of the sample is sprayed into the flame
- The flame separates the sample ions into individual atoms (atomisation) this means
each of the elements have an equal chance of absorbing the light

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 - The elements atoms can absorb some of the light emitted by the lamp, this is because the
emitted wavelength belongs to the element’s emission spectra

3. Monochromator + Slit
- The remaining, unabsorbed light focuses into a beam where it hits the monochromator
- The monochromator and slit selects the wavelength of the element’s emission spectra for
analysis

4. Detector
- The intensity of the light that is incident on the detector is measured
- It compares the original intensity (I0) to the intensity following absorption (I) and
𝐼
measures absorption using the equation 𝐴 = log10 𝐼0
- Absorption is displayed as the final reading

Applications of AAS
- Effective for solutions containing metal ions
- Accurate up to parts per billion can analyse trace concentrations of elements

Determining concentration using AAS

1. Prepare standard solutions (solutions of accurately known concentration)
2. Measure their respective absorbances at a particular wavelength
3. Plot a calibration curve
4. Concentration of sample can be determined via interpolation/extrapolation

Colourimetry
• Measures the concentration of a coloured compound

Principles of Colourimetry
- If white light is passed through a coloured substance, some of the light gets absorbed
- Different substances absorb different wavelengths of light this can be used to identify
the substance
- The amount of absorption is also dependent on the concentration of the solution

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 - Colourimetry is a method of identifying a coloured substance or determining its
concentration in solution based on its ability to absorb parts of the visible
electromagnetic spectrum
- To do this, light of a particular wavelength is absorbed by the solution as it passes
through and the intensity of the light is compared before and after being passed through
the substance being analysed
- For example, when white light is passed through a copper sulfate solution, the
orange/red light is absorbed so the wavelengths that passed through the solution
registers as blue to our eyes
- Groups which absorb light are known as chromophores, each specific chromophore
absorbs a specific range of visible wavelength

- On a colour wheel, the colours opposite to each other are complementary colours
- Mixing two complementary colours form white light
- If a particular colour is absorbed from white light, our eye will detect the
complementary colour
- This concept is important for the principles of colourimetry

1. Light source emits white light

2. Light passes through a lens which focuses the white light into a single beam which passes
through a monochromator
3. The monochromator splits white light into its individual wave length
4. A slit chooses a specific wavelength colour this colour is complementary to the colour
of the solution (a complementary colour is chosen as it will be most strongly absorbed by
the solution)
5. Light (with intensity I0) passes through a sample solution

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 i) Analyte absorbs some of the light
ii) Intensity of the unabsorbed light = I
𝐼
6. Unabsorbed light hits the detector calculates absorbance using 𝐴 = log10 𝐼0

Determining Concentration using Colourimetry:

1. Prepare standard solutions of analyte compounds
2. Measure absorbance at selected wavelength
3. Construct calibration curve: absorbance vs concentration
4. Concentration of sample can be determined using interpolation/extrapolation

The relation of absorbance to concentration is given by Beer-Lambert Law: 𝐴 = 𝜀𝚤𝑐

A = absorbance
ϵ = molar absorption coefficient absorbance under standard conditions (i.e light travelling
through 1cm of a 1mol/L solution)
l = path length (cm) distance travelled by light through sample = width of cuvette
c = molar concentration of solution

Ultraviolet Visible Spectrophotometry

• Measures absorbance in UV-visible range
• Chromophores: atoms responsible for absorbing wavelengths

1. Light source emits light

i) Light is emitted in the UV range (190-750nm)
ii) The light source is either a Deuterium or Tungsten lamp
2. The Diffraction grafting splits the light into distinct wavelengths
3. The slit only allows select wavelengths to pass into the spectrophotometer
4. The light hits the rotation disc, it consists of three sections – transparent, black and
mirrored
i) If the light ray hits the transparent section, it will go straight through and pass
through the cell containing the sample. The unabsorbed light will then hit
another

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 ii) If the light ray hits the mirrored section of the first rotating disc, it is bounced
down and hits a second mirror which allows for the ray to pass through the
reference cell, the unabsorbed light will pass through the transparent section of
the mirror and into the detector
iii) If the light hits the black section of the disc, it is blocked
- The reference cell contains the pure solvent which is used to prepare the sample
- The sample cell contains the solute + the solvent
5. The detector records which wavelengths are absorbed and the amount of absorption at
each wavelength using I and Io

Determining Concentration using UV-vis spectroscopy

1. Prepare standard solutions of the analyte compound use UV-vis to calculate their
absorbance (absorbance is determined at the wavelength of max absorption – this will be
given as the data output)

2. Construct calibration curve

3. Determine the concentration of the sample using interpolation/extrapolation

IQ2: Analysis of Organic Substances

Inquiry Question: How is the information about the reactivity and structure of organic
compounds.

Qualitative investigations to test the presence of organic molecules

Syllabus Dot Point: Conduct qualitative investigations to test for the presence in organic
molecules of the following functional groups:
- Carbon-carbon double bonds
- Hydroxyl groups
- Carboxylic acids (ACSCH130)

Testing for Carbon-carbon double bonds

Classifications:
Alkanes – saturated hydrocarbons only single C-C bonds
Alkenes – unsaturated hydrocarbons at least one double C=C bonds

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Bromine test:

Method:
1. Add 20 drops of bromine water to a clean test tube
2. Add 20 drops of cyclohexane and cover the test-tube with a rubber stopper
3. Add 20 drops of bromine water to a second test-tube
4. Add 20 drops of cyclohexene to the second test-tube and cover with a rubber stopper
5. Gently shake both test-tubes and place them into a test tube rack

Expected observations
- Cyclohexene test-tube results in a colour change from brown to colourless
- The brown colour in the cyclohexane test-tube remains

Reasons for observations

- Cyclohexene can participate in an addition reaction with the bromine forming dibromo-
cyclohexane which is a colourless compound
- Cyclohexane cannot participate in a reaction with bromine in the absence of UV light
meaning that the brown colour will remain

Conditions:
- UV light must be absent

Safety:
- Wear correct PPE
- Keep stock bottles closed and away from heat at all times
- Use a fume cupboard to avoid inhalation of volatile gases from solutions.

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Disadvantages of test
- The test cannot distinguish between alkenes and alkynes
- The test cannot determine the locant of the double/triple bond

Baeyer’s Test

Method:
1. Add 10 drops of KMnO4 to a solution of a particular hydrocarbon
2. Cover with a rubber stopper and gently shake
3. Place the test tube back into the rack allowing for the solution to settle

Observations:
- If a double/triple bond is present, a brown sludge will form, and the solution will
change from purple to colourless
- If a double/triple bond is absent. The purple colour will remain

Reasons for observations:

- KMnO4 can react with alkenes/alkynes forming a colourless diol and the brown solid,
MnO2
- KMnO4 cannot react with alkanes and thus the pink colour persists

Testing for the presence of hydroxyl groups

Classifications:
Monohydric – 1 hydroxyl group
Dihydric – 2 hydroxyl groups
Trihydric – 3 hydroxyl groups
Primary Alcohol – Parent carbon of hydroxyl group is attached to 1 alkyl chain
Secondary Alcohol – Parent carbon of hydroxyl group is attached to 2 alkyl chains
Tertiary Alcohol – Parent carbon of hydroxyl group is attached to 3 alkyl chains

Sodium Metal Test

1. Ensure alcohol is neutral and free of water
2. React sodium metal to dehydrated sample in a test-tube with a rubber stopper

3. If bubbles are formed, perform confirmatory pop-test by removing the stopper and
holding the splint in the test-tube

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 Observations
- If a hydroxyl group is present, bubbles will form in the reaction and a pop will be
heard following the pop test

Reasons for observations

- Alcohols can react with active metals such as sodium
- One of the products of such reaction is the gas, H2
- This gas accounts for the formation of bubbles and the confirmatory pop

Alternate:
4. If solution is evaporated, white sodium ethoxide solid is formed
5. Dissolve the sodium ethoxide in water and test the pH using a pH probe

Observations
- A high pH will be observed indicating the presence of an alcohol

Reasons
- Sodium ethoxide is strongly alkaline solid with a high pH in solution
- Therefore, a high pH indicates the presence of the solid meaning an alcohol reacted with
sodium to form sodium ethoxide

Disadvantages
- The reaction is extremely violent
- The test can only be carried out when the alcohol is free of water and is neutral

Ester Test

Method:
1. In a reflux setup placed in a heating mantle, add potential alcohol, concentrated sulfuric
acid and ethanoic acid
2. Observe the smell of the products

Observations:
- A fruity smell is observed indicating the presence of an ester and consequentially an
alcohol

Reasons for Observations:

- To form an ester, an alcohol must react with a carboxylic acid
- Therefore, if an ester is present, then an alcohol must have been initially present

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Disadvantages
- The test is not entirely conclusive as smell is an inaccurate method of determining a
positive test

Iodoform Test

Method:
1. Mix potential alcohol, Sodium hydroxide solution and iodine in a test-tube
2. Place the test-tube in a 200mL beaker filled to the 100mL graduation mark with water
3. Heat the mixture using a hot plate

Observations
- A yellow precipitate should form in the test-tube indicating the presence of an alcohol

Reasons for observation:

- The alcohol will react with iodine and NaOH and one of the products will be the yellow
precipitate, CHI3

Disadvantages
- The reaction only occurs in ethanol and secondary alcohols

Advantages
- As the reaction only occurs in ethanol and secondary alcohols, it is a suitable test for
differentiating between non-ethanol primary alcohols and secondary alcohols

Oxidation:
Principles:
- Primary Alcohol Aldehyde Carboxylic Acid
- Secondary Alcohol Ketone
- Tertiary Alcohols cannot oxidise

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Differentiating between Tertiary and Primary + Secondary

Method:
1. Dispense 20mL of alcohol into a clean test-tube
2. Add 5 drops of the yellow, acidified potassium dichromate and warm the test-tube in a
hot water bath

Observations:
- A Primary and Secondary alcohol will transition the solution from yellow to green
- A Tertiary alcohol will result in the solution remaining yellow in colour

Reasons for Observation:

- Primary and Secondary alcohols can oxidise which accounts for the colour change
- Tertiary alcohols cannot oxidise and thus the solution will remain yellow

Differentiating between Primary and Secondary:

Method
1. Dispense 20mL of alcohol into a clean test-tube
2. Add 3 drops of the yellow, acidified potassium dichromate to the test-tube
3. Following the formation of an aldehyde or ketone, distil the product to isolate it
4. Dispense the isolated aldehyde or ketone into a test-tube
5. Add 5 drops of the yellow, acidified potassium dichromate and heat in a warm water
bath

Observations
- A Primary alcohol will transition the colour of the solution in the second oxidation from
yellow to green
- A Secondary alcohol is unable to cause a colour change in the second oxidation

Reasons for Observation:

- A primary alcohol can undergo two stages of oxidation which accounts for its ability to
cause a colour change in the second oxidation
- A secondary alcohol can only undergo one stage of oxidation, this means that in the
second oxidation, there will be no colour change as it is unable to oxidise

Alternate1: Tollen’s reagent (colourless solution)

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Method
1. Oxidise alcohol into either ketone or aldehyde in a test-tube
2. Add Tollen’s reagent ([Ag(NH3)2]+)

Observations
- An aldehyde will result in the formation of a mirror like coating
- There will be no colour change in the case of a ketone

Reasons for observation

- An aldehyde can reduce the [Ag(NH3)2]+ into Ag(s) which accounts for the formation of a
silver coating
- A ketone is unable to reduce Tollen’s reagent

Alternate2: Fehling’s solution (blue)

Method
1. Oxidise alcohol into either ketone or aldehyde in a test-tube
2. Add Fehlings solution (complexed Cu2+)

Observations:
- If an aldehyde is present, a brick red precipitate will form resulting in the colour change
from blue to red
- If a ketone is present, no colour change will occur

Reasons for Colour Change

- Aldehyde is able to reduce complexed Cu2+ into the brick red Cu2O(s)

Testing for the presence of carboxyl groups

Classifications
- Aromatic acid – benzene is present sparingly soluble in water
- Aliphatic acid – benzene is not present soluble in water

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Distinguishing Carboxylic acids from other organic compounds:

Litmus Test:
Method:
1. In a test-tube of the organic compound, dip blue litmus paper
2. Observe the colour of the paper

Observation:
- If an acid is present, the blue litmus will turn red
- If another organic compound is present, blue litmus will remain the same colour

Sodium Bicarbonate Test:

Method:
1. In a test-tube of the of the organic compound add a spatula’s amount of NaHCO 3 and
place a rubber stopper with delivery tube over the test-tube
2. Place the delivery tube in a solution of limewater and observe the colour of the limewater

Observations
- If the limewater turns milky and bubbling is observed in the initial test-tube, the organic
compound is a Carboxylic acid

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Reasons for observation
- Acids react with carbonates to produce a salt, water and most importantly, carbon
dioxide

- The carbon dioxide reacts with limewater (Ca(OH)2) to produce the white precipitate,
CaCO3

Ester Test
Method:
1. In a reflux setup, dispense 20mL of ethanol, 20mL of the suspected acid and 5mL of
concentrated sulfuric acid
2. Heat under reflux and observe the smell produced

Observations
- If an acid is present, a fruity smell will be produced

Reasons for Observation

- The fruity smell is indicative of an ester
- Esters are produced by the reaction of an organic acid and an alcohol
- Therefore, if an ester is produced, a carboxylic acid must have reacted and been present

Analysing the structure of organic compounds

Syllabus Dot Point: Investigate the processes used to analyse the structure of simple organic
compounds addressed in the course, including but not limited to:
- Proton and carbon-13 NMR
- Mass Spectroscopy
- Infrared Spectroscopy (ACSCH130)

Mass Spectrometry
Principles:
- If a moving projectile is subjected to a sideways force, it will move in a curve deflected
from its original path
- The magnitude of deflection is dependent on the mass of the projectile

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 - If the speed of the projectile and the magnitude of the force can be calculated, the mass
of the projectile can be found
- In Mass Spectrometry, the projectile is atomic sized particles

Stages of MS:

Stage 1: Ionisation
Inject vaporised sample into ionisation chamber
The atoms in the sample are bombarded with high-energy electrons
The bombardment is able to remove an electron from the valence shell of the atoms in
the sample
Molecules will ionise into molecular ions (M + e- [M]+ + 2e-)
These molecular ions can further fragment into smaller ions
Most of the positive ions formed will carry a +1 charge

Stage 2: Acceleration
The positive ions are repelled from the very positive ionisation chamber
They are passed through an electrical field which only accelerates charged particles
This produces a single focused beam of ions

Stage 3: Deflection
The Accelerated particles are deflected in a magnetic field
Deflection occurs to separate the ions based on mass

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 Amount of deflection depends on:
The charge of the ion
Ions with a greater positive charge (e.g. +2) are deflected more than ions with a
smaller positive charge (e.g. +1)
The mass of the ion
Lighter ions are deflected more than heavier ones
These two factors are combined into the mass/charge ratio using the symbol m/z
Since charge is assumed to be +1, m/z ratio is equal to the mass of the ion

Stage 4: Detection
The detector will only measure the ion current of a specific m/z ratio
Only one specific ion stream is received by the detector
Other ion streams collide with the walls
The walls contain electrons which the ion streams pick up, become neutralised and
are able to be removed via vacuum pump
As positive ions hit the detector, they are neutralised by a flow of electrons and an electric
current is produced
The electric current is recorded
The more ions that arrive = a greater current
To detect other ion currents, the strength of the magnetic field is varied
Some ion streams deflect too much – ions have a smaller mass
Some ion streams don’t deflect enough – ions have a greater mass
This is done on purpose to only allow for one ion stream to reach the detector

Mass Spectrum

Plots relative abundance (%) against m/z

Molecular ion / parent peak = largest m/z
Base peal = tallest peak

Molecular ion peak:

Produced by molecular ion
Largest m/z ratio ion with greatest mass
Produced when the molecule has only lost 1 electron
Therefore m/z corresponds to molar mass
When bombarded with high-energy electrons, any molecular bond on the molecule can be
broken

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 This accounts for the number of peaks with different masses
These peaks represent different sections of the molecule
Base peak
Most abundant fragment (assigned relative intensity of 100%)
Generally most stable
Intensities of all other peaks are relative to the base peak

Effects of isotopes
• Most elements have multiple isotopes which can cause additional peaks in the mass
spectra
• Peaks of isotopes with extremely small abundance (e.g. Hydrogen-2, Carbon-13 &
Oxygen-18) are ignored
• However, some atoms have a relatively significant proportion of each isotope (e.g.
Chrloine-35 and Chlorine-37 or Bromine-79 and Bromine-81) These cause multiple
molecular ion peaks in the mass spectra

Infrared Spectroscopy
Principles:
Bonds of a molecule will vibrate at certain frequencies
Vibrational frequency depends on mass of bonded atoms and the strength of the bond
Heavier atoms vibrate slower – Lighter atoms vibrate faster
Weaker bonds vibrate slower – Stronger bonds vibrate faster
There are two forms of molecular vibrations
Bending
Changes bond angle – can be symmetrical or asymmetrical
Stretching
Changes bond length – can be symmetrical or asymmetrical

Infrared spectroscopy uses infrared radiation to increase molecular vibrations:

When IR radiation is incident on a sample, the atoms in the sample will absorb the radiation
if:
The frequency of the incident photon (infrared light) matches the vibrational frequency
of the bond (the frequency at which the molecule vibrates)
The vibrations that occur changes the overall dipole of the molecule (net distribution of
charge)
Therefore, the molecular vibrations must be asymmetrical in order to achieve a
change in the distribution of charge

• In essence, a light source will shine infrared light through a sample at a number of
frequencies
• At particular frequencies, the molecules in the sample will absorb the radiation
• A detector will measure the absorption at each of the incident frequencies
• This will produce an Infrared Spectra

Infrared Spectra

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 Plots transmittance (%) against wavenumber (cm-1)
Transmittance = amount of light transmitted at each frequency
100% transmittance = no absorption
0% transmittance = 100% absorption
Wavenumber (cm-1) = number of waves per cm
Inverse of wavelength – proportional to frequency

• Strong – “deep” trough less transmittance/greater absorption

• Broad – “wide” trough the bonds absorb IR radiation at a wide range of frequencies

Infrared Spectra for >1400cm-1

Produced by stretching vibrations of the bonds in functional groups
Infrared Spectra for <1400cm-1
Fingerprint Region – produced by bending vibrations
The fingerprint region is unique to each compound

Applications of Infrared Spectroscopy

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 It identifies the different functional groups of a compound
Allows for the differentiation between functional group isomers
(e.g. esters & carboxylic acids)
Can compare the Infrared Spectrum of an unknown compound to a database of known
references
Unknown compound can be identified by matching the unique fingerprint region

Nuclear Magnetic Resonance (NMR) Spectroscopy

Principles of NMR
Uses radio waves to excite nuclei
Radio waves have a long wavelength
Therefore it contains low energy
Due to their low energy, they are unable to cause electronic/vibrational/rotational
transitions
Radio waves cause the nuclei to ‘flip’ between two spin states
To interact with radio waves, the nuclei must have a property called nuclear spin
Only nuclei with an odd atomic number have nuclear spin(e.g. C-13, H-1)
Atomic nuclei can act as small magnets
In the presence of an external magnetic field (B0), nuclei with spin can either align with or
against the field
The magnetic field has a direction
Nuclei that align against the magnetic field (negative spin) have a higher energy state
Nuclei that align in the direction of the field (positive spin) have a lower energy state
Nuclei will naturally align with the magnetic field
Lower energy = more stable

To flip the nucleus into a higher energy state (align against the field)
Radio transmitter emits radio wave photons
The nucleus will absorb the photon
The photon will supply the energy difference between the two spin states meaning
the nucleus can flip into a higher energy spin state

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 Due to the instability of being in a higher energy state, the nucleus will flip back into the
lower-energy spin state
This re-emits the photon in all directions
This photon is detected by an NMR spectrometer

• Resonance condition: the flipping of the nucleus between 2 spin states

• Resonant frequency: the frequency required to flip the nucleus between 2 spin states
• The resonant frequency is dependent on the type of chemical environment

Chemical Environments
• The chemical environment: the atoms and electrons surrounding a specific nucleus

Example: Ethanol:

- 1 carbon is apart of a CH3 group and the other carbon is apart of a CH 2 group 2
carbon environments
- 3 hydrogen atoms are in a CH3 group, 2 hydrogen atoms are in a CH2 group and the
remaining hydrogen is in a OH group 3 hydrogen environments

Example: Propan-2-ol

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 - There are two carbon atoms apart of a CH 3 group that are equidistant from the centre of
the molecule They are apart of the same carbon environment
- There is a remaining carbon which is bonded to an OH group and a hydrogen This
carbon atom is apart of a different carbon environment
- Despite there being 3 carbons, there is only 2 carbon environments
- There is 3 hydrogen environments

• Atoms in the same chemical environment are called equivalent They absorb the same
energy to flip spin states = they produce the same NMR signal

Example: NMR Spectrum

Reference Compound
• Different spectrometers will produce a different magnetic field
• When compounds are analysed in different spectrometers, the same nuclei will emit
different radio frequencies
• Therefore, to compare results from different spectrometers, a reference compound is
needed tetramethyl silane (TMS)

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TMS is used as a reference because:
It is chemically unreactive
It can be easily removed from the analyte compound after measurement
The C & H atoms are a part of the same chemical environment and experience high amounts
of shielding
It will produce a single sharp signal on the far right of the spectrum
TMS will not interfere with the signals of the analyte compound
TMS designates 0 ppm

Chemical Shifts
Chemical Shift (∂): the difference in resonant frequency between the analyte compound and
TMS
Measured in ppm
TMS = 0 ppm
Electrons surround Carbon and Hydrogen nuclei
These electrons are charged & moving particles this induces their own magnetic field
This magnetic field will oppose the direction of the external field this shields the
nuclei
The nuclei will experience a net field that is weaker than the external field due to the
shielding from the electrons
If the C/H nucleus is closer to an electronegative group (e.g. -OH)
The electronegative atom will draw the electron density away from C/H
This makes the nucleus more de-shielded = more exposed to the external magnetic field
Therefore, a higher resonant frequency is required to flip spin states
This results in a larger chemical shift the signal moves downfield (away from TMS
peak)

Carbon-13 NMR Spectroscopy

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 • Focuses on Carbon environments only

Provides two pieces of information:

1. Number of signals indicates the number of different carbon environments
2. Chemical Shift indicates the carbons proximity to electronegative functional groups

Proton NMR Spectroscopy

• Focuses on hydrogen environments only

Provides four pieces of information

1. Number of signals indicates the number of different hydrogen environments

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 2. Chemical shift indicates the carbons proximity to electronegative groups
3. Relative peak area indicates the relative number of H’s per environment
4. Splitting indicates number of H’s in adjacent environments

Relative Peak Area

- The area under the curve of each signal
- This area is proportional to the number of H’s per environment
- To calculate the amount of hydrogen atoms per environment, determine the ratio of
relative peak area among the signals (e.g. 1:3:2:1) and multiply the ratio by the number of
Hydrogens in the molecular formula

Splitting
- The number of splits is the number of peaks produced in a signal
- It can be used to calculate the number of hydrogen atoms in directly adjacent
environments
- The number of splits is 1 more than the number of H’s in the directly adjacent
environments (n+1 rule)
- If neighbouring protons are in the same hydrogen environment, splitting does not occur

Forms of splitting:
- Singlet: produced when there is 0 hydrogens in the neighbouring environments
- Doublet: produced when there is 1 hydrogen in the neighbouring environments
- Triplet: produced when there is 2 hydrogens in the neighbouring environments
- Quartet: produced when there is 3 hydrogens in the neighbouring environments

IQ3: Chemical Synthesis and Design

Inquiry Question: What are the implications for society of chemical synthesis and
design

Overview:
• Chemical Synthesis: Build complex compounds from simpler ones (e.g. NH 3 in the
Haber Process)

Most synthesis reactions apply retrosynthetic analysis

1. Determine desired product
2. Determine suitable reactants
3. Develop a reaction pathway Several factors to consider

Factors affecting reaction pathways

1. Availability and cost of reagents
2. Safety and effectiveness of reaction conditions
3. Yield & Purity of products
4. Industrial uses
5. Environmental, social, and economic issues

Availability of reagents
Sources should be renewable & abundant (e.g. biofuels)

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 Renewable rate of production > rate of consumption
If reagents are sourced from fossil fuels, then the source is not renewable and it
causes a hinderance on the overall synthesis
Transport from location should be time and cost efficient
If the location of the source is far away from the production plant, then there is a greater
transport time and subsequently a greater cost

Reaction Conditions
• Goal: to maximise yield and rate of conversion minimise production costs

For equilibrium systems:

- Constantly remove products shifts equilibrium right
- Recycle unused reactants less waste is produced + increased concentration of
reactants shifts equilibrium right
- Use catalysts (e.g. magnetite (Fe3O4) for Haber Process)

For exothermic unidirectional reactions:

- Reach compromise between rate and yield
- High temperatures are favourable over high pressures as they are cheaper and safer
- To compromise for potential low pressures, use catalysts to increase the rate so a greater
yield will be obtained in a specific duration of time

Yield of Products
• Theoretical Yield: Amount of products formed when all the reactants convert into
products, based on the stoichiometric ratio 100% conversion
Reasons why theoretical yield cannot be achieved
- Equilibrium system is present
- Slow reaction rate
- Reaction species is lost (e.g. purification stage)

Atom economy: the percentage of reactant atoms converted into products higher atom
economy = less wasted reactant atoms

• In an industrial process, atom economy wants to be maximised

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Purity of product(s)
Purity indicates the quality of desired products
High purity is required for pharmaceuticals, fuel and food additives it is required to
remove all by-products
Lower purity can be used for industrial solvents & cleaning products
To achieve high purity, perform synthesis in liquid or gaseous states
It is easier to separate and purify (e.g. fractional distillation)
Non-volatile solids can be dissolved in solution
Detecting Impurities
Mass Spectrometry, NMR or IR Spectroscopy can be used to determine impurities
Quantity of pure product can be calculated using titration or gravimetric analysis

Environmental Issues
Many processes have a high energy demand (e.g. transport, purification)
To have adequate energy, many processes require the burning of fossil fuels. This
releases greenhouse gases and increases the overall carbon footprint
Greenhouse’s gases trap infrared radiation this leads to climate change
Greenhouse gases reduces oxygen levels this is harmful to aquatic life
Ocean acidification occurs

Social Issues
Health issues from exposure to toxic waste
Heavy metal poisoning can occur behavioural abnormalities can form
More automated production (e.g. machines) = less employment can increase
unemployment rate
Improper purification means impurities can be found in the chemicals (e.g. drugs)
Side effects can be experienced
This leads to consumer boycotts

Economic Issues
Synthesis of desired products can generate profits this profits contributes to the economy
Companies want to minimise production costs (e.g. fossil fuels are cheaper to source than
biofuels)
Fossil fuels are more energy dense than biofuels cheaper to run machines as less
amounts of fuel is needed for product synthesis.

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