Module 8 Chemistry | Applying Chemical Ideas

IQ1: Analysis of Inorganic Substances

Inquiry question: How are the ions present in the environment identified and measured?
● analyse the need for monitoring the environment

Basic Information

Pollution: A substance that causes harm to the environment

Water pollution: The alteration in the water quality that negatively affects living organisms or render the water
being unsuitable for desired users
What are the ways that pollution can end up in the environment?
- Spills - Leaching (dissolved by water and
- Industrial waste transported by run-off)
o improper disposal
o emissions into the air

Example/Case Study

Eutrophication: The excessive nutrients in a body of water, caused by frequent runoff from land

Process:
1. Excess use of chemical fertilisers and pesticides (such as insecticides) leads to run-off from farm
irrigation or rain, which results in groundwater contamination within local waterways. The inorganic salts
dissolved in groundwater eventually enter lakes, ponds and rivers.
2. The increased nutrients are absorbed by algae and increased growth of algae reduces sunlight for other
plants
3. Increased decomposition of dead algae uses up oxygen in the water
4. Fish begin to die as oxygen levels fall → anoxic environment
NB: Pesticides are also toxic to fish as it reduces their ability to regulate their internal temperature which
can affect the enzymes’ ability to catalyse necessary metabolic processes like cellular respiration to sustain life
→ More fish die which results in an additional increase in bacteria which will further pollute the environment

Minamata disaster: 1950s - A chemical plant in Japan released chemical waste containing large quantities of mercury →
Led to Minamata disease

● The organisms that were exposed to the large quantities of mercury were affected in many ways. Some
of these included narrow vision, numbness, slurring of speech and, in severe conditions, it resulted in
paralysis, loss of consciousness, convulsions, fever and death.
● As mercury is capable of bioaccumulating like many heavy metals, it means that the mercury is
accumulated in the food chain so that consumption of surviving organisms with appreciable amounts of
mercury could result in death. Many of the fish that resided in the polluted water had high levels of
mercury which were eaten by the unsuspected local population, which resulted in the dangerous health
conditions

Why is it important?
 ● it is important to monitor water quality by determining the amount and type of pollutants that is affecting
the water quality so that the health of living organisms and the condition of surrounding environment can
be maintained at a desirable state

Exam Q: Analyse the implications of eutrophication

● conduct qualitative investigations – using flame tests, precipitation and complexation reactions as appropriate –
to test for the presence in aqueous solution of the following ions:
– cations: barium (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 (for cations only)

Qualitative analysis

Limitations:
o Do not provide any information about the concentration of the cation
o Some metals do not provide a distinctive flame colour and some substances may be dangerous to heat
in an open flame
o Flame tests cannot distinguish the same metals of different valencies (e.g. Fe2+ and Fe3+) because metal
ions regain their valence electrons to become neutral atoms.
o Flame tests cannot detect anions because they are not readily excited by a flame and most do not
release energy in the visible spectrum of light.
o Metals can produce same colour or no colour at all

Procedure:
o A clean wire loop can be dipped into the substance to be tested and then placed over the Bunsen
burner flame.
o Spraying a sample of the substance onto the flame can also be done.

Explanation of observation:
● Electrons become excited when they absorb energy such as heat energy and move up to a higher
energy level and enter an excited state.
● The excited state is specific to the cation – there are no intermediate energies

● Electrons in the excited state are unstable and will return to ground state.

● The energy absorbed is released and emitted as light. The electrons of an atom occupy a number of
different energy levels and hence jumps between these energy levels result in different amounts of
energy being released. The wavelength of a photon released is specific to the cation where the colour
emitted is dependent on the energy of the photon.

Each element has its own unique spectrum because it has its own unique set of energy levels and electron
configuration.

When the electrons move between energy levels, it will involve absorption and emission of different amounts of
energy. This means that every element will emit light of a different set of wavelengths from every other element.
Because every atom of the same element has the same set of energy levels, the pattern produced for an element
will always be the same. This is a way of identifying elements. An unknown element is heated and the light it
emits is analysed and compared with known spectra.

While flame tests are simple to conduct it is sometimes difficult to distinguish between elements that produce
similar colours. For example, barium produces a pale green flame, while copper produces a green flame and zinc
a whitish green flame.

Table 14.2 lists the flame colours of some elements. Magnesium and silver do not produce a coloured flame.
 Metal Flame colour Metal Flame colour

Ba2+ Apple green Fe2+ Gold when very hot, bright blue-green
turning orange-brown

Ca2+ Brick red Fe3+ Orange-brown

Mg2+ None, but for burning Mg metal intense Na+ Yellow

white

Pb2+ Light blue-grey Sr+ Brick red

Ag+ None Li+ Crimson

Cu2+ Blue-green K+ Lilac

Precipitation reactions: Identify certain cations and anions

A precipitate forms when the attraction between two oppositely charged ions in solution is greater than the
attraction between individual ion and water molecules.

→ An insoluble solid will precipitate out of solution

Complexation reactions
● Formation of complex ion

● Complex: combination of a metal (usually transition metal) and one or more smaller molecules called
ligands. Transition metal ions have high charge density and are able to strongly attract ligands (anions
or small polar molecules) to form a complex ion.
● The ligand molecule acts as an electron pair donor to the metal ion, forming a coordinate covalent bond
(i.e. both electrons are donated by the ligand)
● Examples of common ligands are water (H2O), ammonia (NH3), chloride ion (Cl-) and hydroxide ion
(OH-)
● The charge of the complex ion is the same as the charge of the transition metal ion

● The partially negative part of the ligand is orientated towards the central positive metal ion’

E.g. When copper(II) salts are dissolved in water, they generally produce a blue solution and form a complex,
hexaaquacopper(II) ([Cu(H2O)6]2+) with water, as shown in Figure 14.8.

When an aqueous solution of sodium hydroxide is added to the copper(II) solution a pale blue precipitate is
formed. The reaction involves two of the OH− ions replacing two water molecules and the formation of a neutral
compound. The addition of more NaOH has no significant effect on the compound:

[Cu(H2O)6]2+(aq) + 2OH−(aq) → [Cu(H2O)4(OH)2](s) + 2H2O(l) This is usually written more simply as:

Cu2+(aq) + 2OH−(aq) → Cu(OH)2(s)

Identifying anions

Some notable complexation reactions

Complexation Reaction Test for Phosphate Anion

PO43- (aq) + 3NH4+(aq) + 12MoO42-(aq) + 24H+(aq) -> (NH4)3[PO4(MoO3)12](s) + 12H2O(l)

NOTE: (NH4)2MoO4(aq) dissociated into NH4+ and MoO42- ions.

NOTE: (NH4)3[PO4(MoO3)12] has a yellow colour, confirming the presence of phosphate anion.

Complexation Reaction Test for Acetate Anion

A new sample is used and neutral, aqueous ferric chloric is added as the complex ion is not formed under acidic
conditions.

3Fe3+(aq) + 6CH3COO–(aq) + H2O(l) -> [Fe3(OH)2(CH3COO)6]+ (aq) + 2H+(aq)

NOTE: Fe3+ ions came from: FeCl3(aq) -> Fe3+(aq) + Cl–(aq); note that Cl– ion is a spectator ion.

NOTE: [Fe3(OH)2(CH3COO)6]+ is a complex ion with a crimson red colour.

After adding warm and boiling it, a brown-red precipitate forms.

[Fe3(OH)2(CH3COO)6]+ (aq) + 4H2O(l) -> 3Fe(OH)2CH3COO(s) + 3CH3COOH(aq) + H+(aq)

NOTE: Fe(OH)2CH3COO(s) precipitate has a brown-red colour.

● conduct investigations and/or process data involving:

– gravimetric analysis
– precipitation titrations

Gravimetric analysis

Gravimetric analysis: quantitative analysis technique used to determine the proportion, by mass, of a particular
chemical substance in a compound or mixture. The percentage composition of the substance can be determined
The substance to be analysed from the mixture, typically through precipitation

Gravimetric analysis errors:

- Not enough heating → water present in mass → overestimation
Minimise by: drying and weighing until the mass becomes constant
- Loss of mass when transferring
Minimise by: washing equipment with distilled water and minimising the number of transfers.
- Not enough chemicals are added to fully precipitate the ion → incomplete precipitation →
underestimation
Minimise by: using an excess of chemical to form precipitate
- Product can fall through the filter, leading to a loss of mass → underestimation
Minimise by: using suitable filter paper

Gravimetric analysis experiment assumptions:

E.g. precipitating sulfate with barium ions
- Assumes that all the sulfate has dissolved. If they haven’t, the percentage sulfate would be lower as it
would be discarded as residue → low sulfate value
- Assumes excess Ba2+ was added. If not, enough sulfate added, low sulfate value as not all the sulfate
precipitates
- Assumes that precipitate will not pass through the filter paper and become lost → lower sulfate value
- Assumes no soluble phosphates or carbonates are present. These would precipitate with Ba and result
in a higher sulfate value

Advantages and disadvantages of gravimetric analysis

Advantages Disadvantages

● results provide standardised values of the ● Time consuming

substance which are used for instrument ● Prone to errors as stated above
calibration (e.g. use of buffer solutions for
 calibration to test pH)
● May be more accurate than using
instruments to analyse percentage
composition in an analyte

Method

Step 1: Weigh the sample of analyte which you want to measure.

Step 2: Dissolve the sample in water or an alternative, appropriate solvent.

Step 3: Transfer reason amount of precipitate in excess into the solution containing the sample.

Step 4: Flocculate the precipitate using an appropriate method (e.g. heating, slowly mixing the solution, etc).

Step 5: Filter the precipitate using an appropriate method.

Step 6: Wash the precipitate to remove impurities.

Step 7: Dry the precipitate to a constant weight (and sometimes ignite the precipitate) then weigh the precipitate.

Step 8: Repeat step 7 to ensure that the weight is constant.

Precipitation Titrations

● Volumetric analysis that involves a titration where an analyte and titrant react to form a precipitate. A
common precipitating reagent used in precipitation titrations is silver nitrate (AgNO 3)
● Difficulty: Determining the end point as it is difficult to visually tell when a precipitate stops forming.
● For titration to be successfully performed the following factors must be satisfied:
○ precipitate must be quickly formed and be reproducible → limits the amount of impurities that may be
present due to coprecipitation
○ produced precipitate must have low solubility (<5%) → to drive the precipitation reaction as close to
completion as possible in order to have a distinctive change in the ions’ concentration that form the
precipitate at the equivalence point
○ end point must be capable of being identified
● Methods to determine the endpoint of a precipitation titration:

1. Mohr’s method
2. Volgard’s method
3. Fajan’s method

Mohr’s method
Used as a direct titration between a silver nitrate standard solution with chlorides, bromides or cyanides.
Indicator: Potassium chromate K2CrO4 (chromate is yellow in neutral and alkaline conditions)

- If chlorides were used in the titration with the silver nitrate solution, this would first form a precipitate with silver
nitrate:
Ag+(aq) + Cl-(aq) 🡪 AgCl(s)
After all the chloride has been precipitated as white silver chloride, the first excess of the titrant (silver nitrate)
forms a silver chromate precipitate with the indicator:
Ag+ (aq) + CrO42-(aq) 🡪 Ag2CrO4(s)
The formation of the silver chromate precipitate is brick red colour 🡪 determines end point

Error in this titration: an excess of titrant is needed before the end point can become visible. (I.e. the volume of
titrant is not exactly the amount that reacted with Cl-
Overcome error: A blank titration is also carried out where only the indicator and the titrant are present.
Determines the volumes that was in excess. Important to use a constant amount of indicator.

Volhard’s method
Uses back titration to determine concentration of ions such as Cl-, Br-, I-, CN-, PO42-, Cr2O72-, S2- and CO32- in
acidic solution.
However, a direct titration can be used for Ag+
The titration uses Fe3+ as the indicator to detect the end point.
 A known excess of AgNO3 first reacts with the anion X- to form a precipitate:
Ag+(aq) + X-(aq) 🡪 AgX(s)
3+
The precipitate is filtered and removed. Fe is then added to the filtrate as the indicator.
The excess Ag+ are then titrated with a standard solution of thiocyanate ion (SCN -) to form a precipitate:
Ag+(aq) + SCN-(aq) 🡪 AgSCN(s)
When all the Ag has been used up, the first excess of SCN- reacts with Fe3+ to form the red colour complex at the
+

end point.
Fe3+ (aq) + SCN-(aq) 🡪 FeSCN2+ (aq)
red

Fajan’s method
- Fajan’s method is a direct titration, where the end point is determined by an absorption indicator
- The indicator absorbs onto the surface of the precipitate at the end point, causing the colour change
- A specific absorption indicator is needed for a specific pH

Limitations:
- The concentration of the species being analysed cannot be too low, as the amount of precipitate will not
be enough for the indicator to change colour
- A significant amount of non-reacting ions can cause the indicator to coagulate (change to form solid)
with it, resulting in no visible colour change
- Alternatively, the conductivity of a solution can also be measured to determine the equivalence 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 is a sensitive technique used to detect the concentration of substances by analysing the spectrum produced
when the substance absorbs certain frequencies of light.

1. The lamp is made of the 2. A solution of the substance being 3. One wavelength band 4. The absorbance value is
same element being tested is vaporised and (monochromatic) of light shown. The more
tested. Specific atomised (changed into atoms) passes through a slit and concentrated a sample is,
wavelengths of light [is passed through an atomiser to enters the the more light is
characteristic of the heat solution] when being monochromator. This absorbed. Thus, as
element being analysed sprayed onto the flames. measured the intensity of concentration
are emitted by the Note: only the element the light that has NOT increases, absorbance
lamp. tested will absorb the light been absorbed. increases.
emitted from the lamp. Other
elements cannot absorb the
light due to different energy
levels.

Calibration curve is produced to determine the unknown concentration of a sample

A control blank is run which only contains the solvent (zero absorbance)
The absorbance of a number of standard solutions of known concentration for the element being tested is then
measured.
 Advantages Disadvantages

● Very sensitive so can measure trace elements ● Lack of versatility → Geared towards testing
(ppb) → Therefore only a small volume (few liquids rather than solids
mL) of sample solution is required ● Unfeasible for widespread lab use
● Cheap ● Other chemicals founds in the sample or in
● Easy and simple to manipulate machine the surrounding atmosphere can have an
● Highly accurate interfering and distorting effect on the results
● Accessible (e.g. miners can use AAS to
determine the composition of rocks to be
mined)

Colourimetry

NB -
Photometry = Measurement of light intensity
Spectrophotometry = Describes the measurement of the light intensity of a specific wavelength → HENCE
colourimetry is a type of spectrophotometry to examine a specific wavelength/frequency of visible light that is
absorbed by a molecule of concern in a sample to infer the molecule’s concentration

● Used to determine the concentration of COLOURED species

● The intensity of light absorbed is measured
● The lower the intensity of the light exiting, the greater the absorbance, the greater the concentration of
ions in the coloured solution.
● The concentration of an unknown solution can be determined by interpolating the absorbance of a
calibration curve.
● The absorbance value of the test sample can be compared against standardised solutions with
known concentration & absorbance of the molecule/sample of concern using a calibration curve.

In a colourimeter:
1. The light source emits light that is passed through a filter that produces the specific wavelength of the
solution being investigated.
2. The wavelength of the light passes through a glass curvet, which holds the solution being tested.
3. A detector measures the intensity of the light that passes through the solution
4. The amount of light that was absorbed by the solution is displayed.

NB: The filter used should be the complementary colour of the solution to be tested.
E.g. To measure the absorbance of a blue coloured solution, a yellow filter is used to allow the transmission of
yellow light.
The Beer-Lambert Law can also be used to determine the unknown concentration:

A= εlc

A is the absorbance
ε is the molar absorption coefficient (cmmol-1L)
L is the sample cell length (cm)
c is the molar concentration (molL-1)

Note:
The amount of light depends on:
- The substance itself
- The concentration of the sample
- The length of the sample cell
The Beer-Lambert law connects the amount of light absorbed to these factors

Ultraviolet-visible spectrophotometry (broader range)

● UV-visible spectrophotometry uses the UV region (190-400nm) and the visible region (400-900nm) on
the electromagnetic spectrum.
● Compared to a colourimeter, a UV-Vis spectrophotometer uses a diffraction grating or (glass/quartz)
prism to split visible light and ultraviolet radiation into different wavelengths.
● can examine extent of conjugation (a structure of alternating double and single bonds) of the unknown
molecule → Allows determination of structure of molecule which is often used alongside IR and NMR
● Involves moving electrons from the ground state into an excited state. In the spectrometer:
1. A light source provides light of wavelengths 200-800nm
2. The light passes the diffraction grating, which splits the light into different wavelengths.
3. The different wavelengths shine into a reference cell (contains solvent) and the sample cell
(contains sample).
4. The wavelength that absorption occurs, and the amount of absorption is recorded.

Note:
Chromophores: Compounds or parts of compounds that are responsible for UV-visible absorption.
Chromospheres can be colour or not coloured.

IQ2: Analysis of Organic Substances

Inquiry question: How is information about the reactivity and structure of organic compounds obtained?
● conduct qualitative investigations to test for the presence in organic molecules of the following functional
groups:
– carbon–carbon double bonds
– hydroxyl groups
– carboxylic acids

Test for C-C double bond Observation (when positive)

1 Bromine water test In alkanes: the bromine water does not change colour because they do not
react due to the absence of UV light: solution stays brown → with UV, they
would undergo substitution reaction.
In alkenes: the bromine water undergoes addition reactions with the
alkene and thus the bromine decolourises.

Test for carboxyl group Observation (when positive)

1 Test for acidic substance: Litmus turns red.

● Blue litmus *Note: for acidic substances, if we use a red litmus and it remains red,
it would mean the substance could be neutral or acidic.

2 Add sodium carbonate (Na2CO3) Effervescence or bubbling due to the production of CO2 gas:
2CH3COOH(aq) + Na2CO3(aq) → 2NaCH3COOH(aq) + CO2(g) + H2O(l)

Confirmation test for carbon dioxide gas: lime water test.

Ca(OH)2(aq) + CO2(aq) → CaCO3(s) (white ppt) + H2O(l)

Test for hydroxyl group Observation (when positive)

1 React with a small amount of 1. Add CaCl2 to the alcohol to remove water, ensuring that it is
sodium metal dry (sodium and water react violently).
2. Add a small amount of sodium:
2C2H5OH(l) + 2Na(s) → 2C2H5ONa(l) + H2(g)
3. Hydrogen gas can be detected by pop test.
Rate of reaction: primary > secondary > tertiary.

2 Add bromine water No decolourisation (remain red-brown).

3 Ester test: If the resultant product smells fruity, this confirms that the original
Add glacial acetic acid with 2-3 sample contains an alcohol.
 drops of concentrated sulfuric acid *Note: performed under reflux because any direct flame can combust any
in a warm bath for 30 minutes alcohol present → dangerous.
(esterification)

4 Add acidified potassium dichromate Turns the dichromate solution from orange to green if it is a primary or
under reflux secondary alcohol.

5 Add acidified potassium Turns permanganate solution from deep purple to colourless if it is a
permanganate under reflux primary or secondary alcohol.
*Note: not reliable as dichromate

6 Add ZnCl2/HCl (Lucas’ reagent) ● Tertiary alcohol produces a cloudy bottom layer immediately
● Secondary alcohol produces a cloudy bottom later slowly
● Primary alcohol do not produce a cloudy bottom layer

To distinguish between primary and secondary

alcohols, Schiff’s reagent can be used.
Small amounts of aldehyde (from oxidation of primary
alcohol) turns Schiff’s reagent from colourless to magenta.

● 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 spectrometry
– infrared spectroscopy

Organic Spectrometry
● To determine the structure of organic compounds, information is obtained from a variety of analytical
techniques
 ● The instruments use a certain range of the electromagnetic spectrum and corresponds to the energy
used by the technique

Technique Energy Source Data Output

Mass spectrometry High-energy electrons Peaks correlating to the m/z ratio that indicate the
molar mass and isotopic abundance
NMR spectroscopy Radio waves Peaks that are useful for determining the C-H
backbone of a molecule
IR spectroscopy Infrared waves Bands used to determine the type of bonds and
functional groups present. May identify the
compounds using spectra as ‘fingerprints’
UV-vis spectroscopy UV-visible waves Absorption spectra that show the concentration of
organic compounds. May identify the compounds
using spectra as ‘fingerprints’

Mass Spectrometry
Provide information on the molar mass of an element present or detect isotopes of elements.
 IONISATION
● In the ionising chamber, an atom or molecule is ionised using high energy electrons.

● A single electron from the molecule is removed to form a positively charged

molecular ion (a radical cation – unpaired electron)
● Due to the collision, the resulting ion has a high kinetic energy and can break down
further into fragment ions

ACCELERATION
● These positive particles are accelerated along the path by an electrical field
DEFLECTION
● As the particles pass through a magnetic field, they get deflected based on mass
(m) to charge (z)
● The lower the mass and the higher the charge, the more the ion will deflect

● Neutral fragments will not be deflected

DETECTION
● The ions, separated by mass, are collected by the detector

● The intensity of the ion beam provides a measure of abundance, overall producing a
mass spectrum
Note: Only cations are detected

o Each peak obtained is due to a fragment with a certain m/z ratio

o Position of the peak provides information about the molecular mass of a substance
o Molecular ion: highest m/z value
o Base peak: most intense (tallest) peak with an abundance of 100%
o Tallest peak is from the most stable species

Infrared Spectroscopy
● Used to determine the bonds or functional groups in organic
compounds
● Covalent bonds have different strengths and vibrate at different
frequencies
● In IR spectroscopy, covalent bonds in molecules absorb energy
from the IR region and is excited to different vibrational motions
● Various types of vibrations are: bending, stretching or twisting,
wagging and rocking

Note: For a molecule to be detected, there must be a change in dipole

moment as the results of the vibration when IR radiation is absorbed (the
molecule is IR active)
Molecules that cannot be detected include:
o Diatomic molecules (e.g. O2, N2)
o Stretching vibrations of symmetrical double and triple bonds

Infrared spectrophotometer
● A beam of infrared radiation is passed through the sample

● A similar beam is passed through the reference cell (containing the solvent)

● The frequency of radiation is separated in the monochromator. Bonds vibrating with a similar frequency
absorb the radiation
 ● The amount of radiation absorbed by the sample is compared with the reference

● The results are collected, stored and plotted

- Frequency of radiation is usually expressed as wavenumber (cm-1)

- The transmittance (%) shows the amount of radiation that passed through the sample (i.e. absorbance
bands show the radiation absorbed)

Fingerprint region
Absorbance bands above 1400cm-1 are
used to identify functional groups, while
regions below 1400cm-1 is called
fingerprint region as it is unique to each
compound
 Carbonyl compounds
Show a sharp, strong absorption
between 1700cm-1 and 1760cm-1
Due to presence of C - - O

Alcohols
Show a broad absorption between
3200cm-1 and 3600cm-1
Due to presence of a O-H bond

Carboxylic acids
Show a broad absorption between 3200
and 3600cm-1, due to O-H bond
A strong absorption at around 1700cm-1
is also shown due to the C - - O bond

Esters
Show a strong absorption between 1750
and 1730cm-1

NMR Spectroscopy
 ● Nuclear magnetic resonance (NMR) spectroscopy uses
radio waves to help determine the structure of a
molecule.
● Many atomic nuclei possess an intrinsic property called
spin (or angular momentum)
● Spin is the rotation of electrically charged nucleus about
their own axis, which generates a magnetic field and
hence, carries a magnetic moment
● A nucleus that possess spin must either have:
o An odd mass number
o An odd atomic number
● A nucleus without spin cannot be detected NMR

▪ In an NMR spectrometer, the sample is spun

round in a field of an electromagnet and a radio
frequency is applied
▪ The magnetic field is increased and the
excitation/flipping of nuclei from one orientation to
another is detected

o The larger the strength of the external magnetic field, the bigger the difference in energy between the
two states

- Most nuclei will be in a low energy spin state

- The radio transmitter will provide energy so that the nuclei ‘flips’ into a higher energy state
- The nuclei will eventually return to the lower energy state and emit a pulse of energy

Chemical shift (ppm): energy required to change spin

This amount of energy is unique to the:
- nucleus
- chemical environment
 ● Electrons also have a spin and can shield the nucleus from experiencing the full effects of the magnetic
field.
● The hydrogen near oxygen will be more deshielded as oxygen is an electronegative species has a high
ability to draw electrons and hence is electron rich whilst the hydrogen atom is electron poor.
● The more exposure to a magnetic field, the more energy it takes to spin flip.

● The closer H’s are to an electronegative species, the higher the chemical shift

H NMR - TMS or tetramethylsilane (CH3)4Si is added to provide a reference signal

Provides information - A liquid sample is placed in the tube
about the hydrogen - The solids are dissolved in deuterated solvents (e.g. deuterated
atoms in a molecule chloroform, CDCl3) or solvents without H’s (CCl4)
- Chemical shift: 0
Low resolution NMR - Gives a peak for each environmentally different group of protons
- The ratio of the areas under the peaks 🡪 number of hydrogen atoms in
that environment
High resolution NMR - Shows the same information as the low resolution spectrum but each
signal is further split into a number of peaks
- Number of neighbouring hydrogens = number of peaks – 1 (n+1 rule:
number of peaks = number of chemically different H’s on adjacent atoms +
1)

Feature Information it provides

Location/number of signal groups The number of different proton environments
Chemical shift The general environment of the protons
Peak area/integration The number of protons in each environment
Splitting/multiplicity The number of protons on neighbouring atoms

C NMR Only the chemical shift is important as each spectrum only gives single lines for
each chemically equivalent carbon
The number of peaks indicate the number of different carbon atom environments
Equivalent carbon atoms produce signals with the same chemical shift
Note: height of the peak does NOT relate to the number of carbons in each
environment.