Contents

Chapter No. Chapter Name Page No.

Atomic Structure 3

The structure of an atom in terms of sub atomic mass and particles 3

The role and function of isotopes 15

The function of a mass spectrometer

16

02 Mole Calculations

ATOMIC STRUCTURE

1. Atomic structure

The basis of chemistry is atoms, which are fundamentally empty spaces. Approximately
all of an atom’s mass is restricted in its tiny nucleus, which is surrounded by far-off
electrons.

The diameter of an atomic nucleus is of the category of 10-15m, while the size of the
atom is around 10-10 m. So the nucleus is 1/100000 times smaller than the atom.

1.1 The subatomic particles

1.2
Atoms are made of three fundamental particles protons, neutrons, and electrons.
The protons and neutrons form the nucleus, in the center of the atom.

Protons and neutrons are sometimes called nucleons because they originate in the
nucleus. The electrons encircle the nucleus in shells of increasing radius.

1.3 The distribution of mass and charge

1.4
The properties of the subatomic particles are shown in the table below.

Property Proton p Neutron n Electron e

Mass /kg 1.673× 10-27 1.675× 10-27 0.911× 10-30

Charge /C +1.60× 10-19 0 -1.60× 10-19

Position In the nucleusIn the nucleusaround the nucleus

These numbers are tremendously small. In observation, relative values for mass and
charge are used. The relative charge on a proton is taken to be +1, so the charge on an
electron is -1, Neutrons have no charge (see Table below).

Proton p Neutron n Electron e

Relative mass 1 1 1/1840

Relative charge +1 0 -1

In a neutral atom, the number of electrons is necessary to be the same as the number of
protons for the reason that their charge is equal in size and contradictory in sign.

1.3 Atomic number and mass number

Atoms consist of tiny nuclei made up of protons and neutrons that are surrounded by
electrons.

Proton number Z (atomic number)

The number of protons in the nucleus is called the atomic number or the Proton number.
It is represented by Z. The proton number is equal to the number of electrons in the
atom, so atoms are electrically neutral. The chemical properties of an element (how it
reacts) and what sort of element it depends upon the number of electrons in the outer
shell. The atomic number defines the chemical identity of an element.

vAtomic number Z = number of protons

All atoms of the same element have the same atomic number. Atoms of different elements
have different atomic numbers. It is the proton number that defines a particular element.

Mass number A

The total number of protons plus neutrons in the nucleus (the total number of nucleons)
is called the mass number. It is represented by A. This is also called the nucleon number,
as both protons and neutrons are nucleons.

Mass number A = number of protons Z + number of neutrons N

The number and electrons is the same in a neutral atom. In a positive ion, electrons are
less than protons as one or more electrons have been lost. In a negative ion, more
electrons than protons are present the reason is that one or more electrons have been
gained, so there are more electrons than protons.

For example, in a sodium atom (Z = 11, A = 23) there are 11 protons, 11 electrons, and 12
neutrons. In a Na+ ion, there are 11 protons, 10 electrons, and 12 neutrons.

In a fluorine atom (Z =9, A = 19) there are 9 protons, 9 electrons, and 10 neutrons. In
fluorine ions, there are 9 protons, 10 electrons, and 10 neutrons.
 1.5 Electron proton and neutron in an atom
1.6
In the figure below the subatomic particles (protons, neutrons, and electrons) are shown
which are arranged in the atom. In the center of the atom (the nucleus), proton and
neutron are held together by a force called the strong nuclear force. This is much
stronger than the electron the electrostatic force of attraction that holds electrons and
protons mutually in the atom, so it overcomes the repulsion between the protons in the
nucleus. It acts only over very small distances within the nucleus. Electrons surround the
nucleus. Electrons are found in a sequence of energy levels, also referred to as orbits or
shells, which get further and further away from the nucleus.

1.5 Relative atomic masses

The relative atomic mass of an element is the average mass of an atom of the element
relative to one-twelfth the mass of an atom of the isotope carbon-12 is called the relative
atomic mass of an element.

The symbol for relative atomic mass is Ar, where ‘r’ stands for relative.

Relative atomic mass = average mass of an atom of the element divided by 1/ 12 × the
mass of one atom of carbon-12

Relative isotopic mass

Relative isotopic mass is the mass of one atom of an isotope relative to 1/ 12th of the
mass of an atom of the isotope carbon-12.

The values are relative so they do not have units.

Relative molecular mass

The relative molecular mass of an element or compound is the sum of the relative atomic
masses of all the atoms in its molecular formula.
Relative formula mass

The relative formula mass of a compound is the sum of the relative atomic masses of all
the atoms in its formula is called relative formula mass.

Orbital

The electron is no longer well thought-out to be a particle but a cloud of negative charge.
An electron fills a volume in space called its atomic orbital. The concept of the shells and
the sub-shells is then included in the following way.

Different atomic orbital have, unlike energies. Each orbital has a number that tells
us the main energy level that it corresponds to 1, 2, 3, and so on.

Each shell of an atomic orbital has different shapes, which in twist have to some
extent different energies.

These are the sub-levels. They are described by the letters s, p, d, and f. The
shapes of the s, p, and d-orbital are shown in the figure on the left side. The shapes of f-
orbital are even more complicated.

These shapes are a symbol of a volume of space in which there is a 95% possibility
of discovery of an electron and they manipulate the shapes of molecules, the first most
important energy level consists of a single s-orbital. The second shell has a single s-
orbital and three p-orbital of a to some degree higher energy, the third shell has a single
s-orbital, three p-orbital of to some extent advanced energy, and lived-orbital of slightly
higher energy still, and so on (see Figure below).

Any single atomic orbital can grasp a maximum of two electrons.

 s-orbital can hold up to two electrons.

p-orbital can hold up to two electrons each, but always approach in groups of
three of the same energy, to give a total of up to six electrons in the p-sub-level.

d-orbital can hold up to two electrons each, but come in groups of five of the same
energy to give a total of up to 10 electrons in the d-sub-level.

1.7 Electronic structure

1.8
In the currently acknowledged model of the atom, electrons have permanent energies.
They are in motion around the nucleus in certain regions of the atom called shells or
energy levels. Experiments give you the idea that not all the electrons in a shell have the
same energy. The atomic model explains these shells are alienated up into sub-shells.
Different electron shells have different numbers of sub-shells, which each have a
different energy. Sub-shells can be s sub-shells, p sub-shells, d sub-shells, or f sub-shells.

Orbital and the Periodic Table

The array of elements in the Periodic Table reflects the electronic structure of the
elements.

Elements in Groups I and II have outer electrons in an s sub-shell.

Elements in Groups III to 0 (apart from He) have outer electrons in a p sub-shell.

Elements that add electrons to the d sub-shells are called the d-block elements.
Most of these are transition elements.

1.9 Electronic configurations

1.10
A comprehensive way of writing the electronic configuration of an atom which includes
information about the number of electrons in each sub-shell is shown below for
hydrogen.

Helium has two electrons. Both electrons can depart into the 1s orbital since this
can grasp a maximum of two electrons. So, the electronic structure of helium is 1s2.

Lithium has three electrons. The maximum of two electrons are held by the 1s
orbital. So the third electron must go into the next highest sub-shell, that is must be 2s.
So, the electronic structure of lithium is 1s2 2s1. Electrons are added one by one for
subsequent elements, filling each sub-shell in order of increasing energy.

The electronic configurations of the elements up to 36 electrons

Element number Symbols Electronic configuration

1 H 1s1

2 He 1s2

3 Li 1s2 2s1

4 Be 1s 2 2s 2

5 B 1s 2 2s 2 2p1

6 C 1s 2 2s 2 2p2

7 N 1s 2 2s 2 2p3

8 O 1s 2 2s 2 2p4

9 F 1s 2 2s 2 2p5
10 Ne 1s 2 2s 2 2p6

11 Na 1s 2 2s 2 2p6 3s1

12 Mg 1s 2 2s 2 2p6 3s2

13 Al 1s 2 2s 2 2p6 3s2 3p1

14 Si 1s 2 2s 2 2p6 3s2 3p2

15 P 1s 2 2s 2 2p6 3s2 3p3

16 S 1s 2 2s 2 2p6 3s2 3p4

17 Cl 1s 2 2s 2 2p6 3s2 3p5

18 Ar 1s 2 2s 2 2p6 3s2 3p6

19 Potassium (K) [Ar] 4s1

20 Calcium (Ca) [Ar] 4s2

21 Scandium (Sc)[Ar] 3d1 4s2

24 Chromium (Cr) [Ar] 3d5 4s1

25 Manganese (Mn) [Ar] 3d5 4s2

29 Copper (Cu) [Ar] 3d10 4s1

30 Zinc (Zn) [Ar] 3d5 4s2

31 Gallium (Ga) [Ar] 3d5 4s2 4p1

35 Bromine (Br) [Ar] 3d5 4s2 4p5

36 Krypton (Kr) [Ar] 3d5 4s2 4p6

1.9 Orbital diagram

Electrons in the same region of space repel each other because they have the same
charge. So wherever possible, electrons will occupy separate orbitals in the same sub-
shell to minimize this repulsion. The electrons have their ‘spin’ in the same direction.
Electrons are only paired when there are no more empty orbitals available within a sub-
level. The spins are then opposite to minimize repulsion. The figure below shows the
electronic structures of carbon, nitrogen, and oxygen to illustrate these points.

1.11 Shapes of s and p orbital

1.12

1.11 Ionisation energy

Ionization energy is the energy that has to be put in to form positive ions. Energy is given
out when negative ions form. This is called electron affinity. The attraction between the
nuclear charge and the electrons in the outer shell of an atom has a result which is known
as ionization energy. The patterns in first ionization energies transversely a period
provide evidence for electron energy sub-levels.
 Electrons can be removed from atoms and the energy it requires to remove them
can be measured. This is called ionization energy because as the electrons are removed
the atoms become positive ions. Ionization energy is the energy required to remove a
mole of electrons (a mole of atoms in the gaseous state and is measured in kJ/mol. )

Ionization energy has the short form IE.

Removing the electrons one by one (successive ionization energies)

The energies required to remove the electrons one by one from an atom can be measured
in this way, starting from the outer electrons and working inwards.

The least energy is required by the first electron for removal because it is being
removed from a neutral atom. This is the first TE.

The reason for more energy requirement for second electron removal is just
because it is being removed from a +1 ion. This is the second TE.

The third electron needs even more energy to remove it because it is being
removed from a +2 ion. This is the third IE.

The fourth needs yet more energy, and so on.

These are called successive ionization energies.

1.13 Equation for 1st 2nd and 3rd ionization energies

1.14
Na(g) → Na+(g)+ e- first IE = +494 kJ /moll

Na+(g) → Na2+(g)+ e- second IE =+ 4560 kJ /mol

Na2+(g) →Na3+ (g)+ e- third IE =+ 6940 kJ /mol

Successive ionization energy table

Electron
Removed 1st 2nd 3rd 4th 5th 6th 7th 8th 9th 10th

IE(kg/mol)

494 4560 6940 9540 13352 16611 20115 25491 28934 141367

1.15 plot of ionization energy versus number of electrons

1.16
Plot a graph of the values shown in the Table above, the result of this is the graph shown
in Figure aside. Notice that one electron is comparatively easy to remove, then comes a
group of eight electrons that are more difficult to remove, and finally two electrons that
are very difficult to remove.

This suggests that sodium has:

One electron furthest away from the positive nucleus (easy to remove)

Eight electrons nearer the nucleus (harder to remove)

Two electrons very close to the nucleus (very difficult to remove because they are
nearest to the positive charge of the nucleus).

This tells you about the number of electrons in each shell or orbit: 2,8,1. The eight
electrons in shell 2 are subdivided into two. Looking at the jumps in successive ionization
energies the number of electrons in each shell can be determined.

1.14 Trends in ionization energies down a group in the Periodic Table

`In the Figure below it is shown that there is a general decrease in first ionization energy
going down Group 2 and the same pattern is seen in other groups, This is because the
outer electron is in a shell that gets away from the nucleus in each case. So as the atomic
radius increases, the ionization energy decreases. The outer electrons in each atom in the
same group feel the same nuclear charge, altering taking into account the shielding of the
inner electrons.

The nuclear charge rises with a group down. An electron removal process might seem
more challenging as a result of this at first. A positive charge in the outer shell, however,
is not actually “felt” by an electron in its entirety. The reason for this is the nuclear
charge’s shielding effect provided by the inner electrons.

1.15 plot of ionization energy versus number of electrons

Na Mg Al Si P S Cl Ar

494 739 577 786 1060 1000 1260 1520

Nuclear charge increasing ------------------------------------------------→

Plot a graph of the values shown in the Table above, the result of this is the graph shown
in Figure aside. Notice that one electron is comparatively easy to remove, then comes a
group of eight electrons that are more difficult to remove, and finally two electrons that
are very difficult to remove.

This suggests that sodium has:

One electron furthest away from the positive nucleus (easy to remove)

Eight electrons nearer into the nucleus (harder to remove)

Two electrons are very close to the nucleus (very difficult to remove because they
are nearest to the positive charge of the nucleus).

This tells you about the number of electrons in each shell or orbit: 2,8,1. The eight
electrons in shell 2 are subdivided into two. Looking at the jumps in successive ionization
energies the number of electrons in each shell can be determined.
 1.17 Successive ionisation energies
1.18
The energies required to remove the electrons one by one from an atom can be measured
in this way, starting from the outer electrons and working inwards.

The least energy is required by the first electron for removal because it is being
removed from a neutral atom. This is the first TE.

The reason for more energy requirement for second electron removal is just
because it is being removed from a +1 ion. This is the second TE.

The third electron needs even more energy to remove it because it is being
removed from a +2 ion. This is the third IE.

The fourth needs yet more energy, and so on.

These are called successive ionization energies.

Isotopes

All atoms of the same element have the same number of protons. However, they may
have different numbers of neutrons. Atoms of the same element which have different
numbers of neutrons are called isotopes.

2.2 chemical properties concerning isotopes

Because they have the same electronic configuration, different isotopes of the same
element react chemically in precisely the same ways. Because the nuclei of different
isotopes of the same element have different numbers of neutrons, the nucleon number of
those atoms varies. Because they have different masses, different isotopes of the same
element have different physical properties. Since the atoms’ sizes are identical, this
implies that their densities are also different.
2.3 Symbols for isotopes

We can write symbols for isotopes. We write the nucleon number at the top left of the
chemical symbol and the proton number at the bottom left. The symbol for the isotope of
boron with 5 protons and 11 nucleons is written:

Hydrogen has three isotopes. The atomic structure and isotopic symbols for the three
isotopes of hydrogen are shown in Figure below.

Mass Spectrometer

A mass spectrometer is a machine used to analyze elements or compounds.

How a mass spectrometer works

When used for compound analysis, a mass spectrometer can provide information on the
relative molecular mass of a molecule as well as the relative atomic mass and isotope
abundance of an element. A sample squirted into a mass spectrometer causes the
following four outcomes:

Ionization

The sample needs to be ionized before it enters the mass spectrometer. Two way of
doing this is Electrospray ionization, In this method, the sample is dissolved in a solvent
and pushed through a small nozzle at high pressure. It receives a high voltage, which
adds an H+ ion to each particle. After that, the solvent is eliminated, leaving a gas
composed of positive ions.
Electron impact ionisationUsing an “electron gun,” high energy electrons are fired at the
sample to cause it to evaporate in this procedure. As a result, each particle loses one
electron, making them become +1 ions.

Acceleration

An electric field accelerates the positive ions. Every ion receives the same kinetic energy
from the electric field. Even though the lighter ions receive the same amount of energy as
the heavier ions, their acceleration is greater because they are lighter.

Ion drift

The ions then move into an area devoid of an electric field. Just as they left the electric
field, they drifted through it at the same speed. As a result, the lighter ions will drift
faster.

Detection

Lighter ions arrive at the detector faster than heavier ions because they move through
the drift region more quickly. When ions strike the detector, a current is generated, and
the duration of the ions’ passage through the spectrometer is recorded. The mass/charge
values required to generate a mass spectrum are then computed using this data.

3.2 & 3.4 Interpreting a mass spectrum

A mass spectrum is a type of chart produced by a mass spectrometer. It shows

information about the sample that was passed through the mass spectrometer.

Each line in the sample, assuming it is an element, will stand for a distinct isotope of that
element (see Figure below). The y-axis displays the ion abundance, frequently expressed
as a percentage. The relative isotopic abundance of an element is determined by the
height of each peak, which represents the proportion of each isotope in a sample. The
units on the x-axis are expressed as a “mass/charge” ratio.
The mass spectrum produced when a sample of lithium is passed through a mass
spectrometer is shown below.

There are two peaks, so the sample contains two isotopes of lithium. One peak has a
mass/charge ratio of 6, so the relative isotopic mass of one isotope is 6. (Since the lithium
ions produced in a mass spectrometer have a charge of 1+ (Li+ ) and 6 ÷ 1 = 6.) The other
peak has a mass/charge ratio of 7, so the relative isotopic mass of the other isotope is 7.
So, from the mass spectrum, you can tell that there are two isotopes present, 6Li and 7Li.
92.4% of the sample is 7Li. 7.6% of the sample is 6Li.

3.3 Identifying elements

Mass spectrometry can be used to identify elements.

Element identification can be done via mass spectrometry. Because various isotopes have
varying masses, elements with distinct isotopes create many lines in a mass spectrum.
This results in distinctive patterns that serve as “fingerprints” for identifying particular
components.

Magnesium has three isotopes with the percentage abundances shown in the table below.
If a sample being analyzed contains magnesium, this isotopic distribution will show up in
the mass spectrum.

Mg isotopes % Abundance

24 Mg 79

25 Mg 10

26 Mg 11
Calculating relative atomic mass

It is important to know how to calculate the relative atomic mass (Ar ) of an element from
a mass spectrum.

Step 1: For each peak, read the % relative isotopic abundance from the y-axis and the
relative isotopic mass from the x-axis. Multiply them together to get the total relative
mass for each isotope.

Step 2: Sum up these totals.

Step 3: Divide by 100 (since percentages were used).

Example

Here’s how to calculate Ar for magnesium, using the mass spectrum below:

Step 1:

Total mass of 1st isotope: 79 × 24 = 1896

Total mass of 2nd isotope: 10 × 25 = 250

Total mass of 3rd isotope: 11 × 26 = 286

Step 2:

1896 + 250 + 286 = 2432 Step 3: 2432 ÷ 100 = 24.32 So Ar (Mg) = 24.3 (to 3 s.f.)

Mole calculations

1.1 Empirical Formula and molecular formula

1.2
Empirical Formula:

The simplest whole number ratio of the elements contained in a single molecule or compound
formula unit is known as empirical formula of that compound.

Molecular Formula:

The molecular formula displays the precise quantity of every distinct atom that makes up a
molecule. The empirical formula is not as helpful as the e molecular formula. Molar masses and
balanced equations can be computed using the molecular formula. Every time, the empirical
formula is multiplied by the e molecular formula.

1.3 Calculation of empirical formulae using combustion data.

1.4
Calculation

When 1.55 g of phosphorus is completely combusted 3.55 g of an oxide of phosphorus is

produced. Deduce the empirical formula of this oxide of phosphorus.

(Ar values: O = 16.0, P = 31.0)

 P O

Step 1 Note the mass of each element 1.55 g 3.55 – 1.55 = 2.00 g

Step 2 Divide by atomic masses 1.55g/31.0 g mol-¹

=0.05g mol 2.0g/16.0g mol -¹

=0.125 mol

Step 3 Divide by the lowest figure 0.05/0.05 = 1 0.125/0.05 = 2.5

Step 4 If needed, obtain the lowest whole number ratio to get empirical formula P2O5

1.3 Calculation of molecular formulae from empirical formulae and Mr values.

A compound has the empirical formula CH2 Br. Its relative molecular mass is 187.8. Deduce the
molecular formula of this compound. (Ar values: Br = 79.9, C = 12.0, H = 1.0)

Step 1 find the empirical formula mass: 12.0 + (2 × 1.0) + 79.9 = 93.9

Step 2 divide the relative molecular mass by the empirical formula mass: 187.8 /93.9 = 2

Step 3 multiply the number of atoms in the empirical formula by the number in step 2: 2 × CH2
Br,

So molecular formula is C2H4Br2.

1.5 Construction of balanced chemical equations.

1.6
Balancing chemical equations

Atoms cannot be created or destroyed during a chemical reaction. Therefore, in a chemical

equation, the number of each type of atom on the reactant side must equal the number on the
product side. A chemical reaction can be concisely described using a symbol equation. Both the
quantity and kind of atoms in the reactants and the quantity and kind of atoms in the products
are displayed. We declare the equation balanced if these are equal. To understand how we
balance an equation, consider these examples.

Balancing an equation

Step 1 Write down the formulae of all the reactants and products. For example:

H2 + O2 → H2O

Step 2 Count the number of atoms of each reactant and product.

H2 + O2 → H2O

2[H] 2[O] 2[H] + 1[O]

Step 3 Balance one of the atoms by placing a number in front of one of the reactants or products.
In this case the oxygen atoms on the right-hand side need to be balanced, so that they are equal
in number to those on the left-hand side. Remember that the number in front multiplies
everything in the formula. For example, 2H2O has 4 hydrogen atoms and 2 oxygen atoms.

H2 + O2 → 2H2O

2[H] 2[O] 4[H] + 2[O]

Step 4 Keep balancing in this way, one type of atom at a time until all the atoms are balanced.

2H2 + O2 → 2H2O

4[H] 2[O] 4[H] + 2[O]

Note that when you balance an equation you must not change the formulae of any of the
reactants or products.

1.5 Ionic equations from chemical equations.

Balancing ionic equations:

 When ionic compounds dissolve in water, the ions separate from each other. A complete
chemical equation is more complicated than an ionic equation. It displays only the reacting ions
or other particles.

Writing an ionic equation

Step 1 Write down the full balanced equation.

Mg(s) + 2HCl(aq) → MgCl2 (aq) + H2 (g)

Step 2 Write down all the ions present. Any reactant or product that has a state symbol (s), (l) or
(g) or is a molecule in solution such as chlorine, Cl2 (aq), does not split into ions.

Mg(s) + 2H+(aq) + 2Cl−(aq) →Mg2+(aq) + 2Cl−(aq) + H2 (g)

Step 3 Cancel the ions that appear on both sides of the equation (the spectator ions).

Mg(s) + 2H+(aq) + 2Cl−(aq) → Mg2+(aq) + 2Cl−(aq) + H2 (g)

Step 4 Write down the equation omitting the spectator ions.

Mg(s) + 2H+(aq) → Mg2+(aq) + H2 (g)

1.7 Mole calculations using chemical equations and:

1.8
i. Reacting masses

Magnesium burns in oxygen to form magnesium oxide.

2Mg + O2 → 2MgO

We can calculate the mass of oxygen needed to react with 1 mole of magnesium. We can
calculate the mass of magnesium oxide formed.

Step 1 Write the balanced equation.

Step 2 Multiply each formula mass in g by the relevant stoichiometric number in the equation.

2Mg + O2 → 2MgO

2 × 24.3 g 1 × 32.0 g 2 × (24.3 g + 16.0 g)

48.6 g 32.0 g 80.6 g

From this calculation we can deduce that:

■ 32.0 g of oxygen are needed to react exactly with 48.6 g of magnesium

■ 80.6 g of magnesium oxide are formed.

If we burn 12.15 g of magnesium (0.5 mol) we get 20.15 g of magnesium oxide. This is because
the stoichiometry of the reaction shows us that for every mole of magnesium burnt we get the
same number of moles of magnesium oxide.

ii. Volumes of gases (using the molar volume of a gas)

Calculate the mass of anhydrous copper(II) sulfate in 55 cm3 of a 0.20 mol dm–3 solution of
copper(II) sulfate.

(Ar values: Cu = 63.5, O = 16.0, S = 32.1)

Step 1 Change cm3 to dm3.

=55/1000 = 0.055 dm3

Step 2 moles = concentration (mol dm–3) × volume of solution (dm3)

= 0.20 × 0.055 = 0.011 mol

Step 3 mass (g) = moles × M

= 0.011 × (63.5 + 32.1 + (4 × 16.0))

= 1.8 g (to 2 significant figures)

iii. Volumes and concentrations of solutions

Calculate the concentration in mol dm–3 of sodium hydroxide, NaOH, if 250 cm3 of a solution
contains 2.0 g of sodium hydroxide. (Mr value: NaOH = 40.0)

Step 1 Change grams to moles.

2.0 / 40.0 = 0.050 mol NaOH

Step 2 Change cm3 to dm3.

250 cm3 = 250 / 1000 dm3 = 0.25 dm3

Step 3 Calculate concentration.

0.050 (mol) / 0.25 (dm3) = 0.20 mol dm–3

1.7 Calculate percentage atom economy and percentage yields from chemical equations.

Percentage yield

Percentage yield = actual yield /theoretical yield × 100%

A modern gas-fuelled lime kiln produces 500 kg of calcium oxide, CaO (quicklime), from 1000 kg
of crushed calcium carbonate, CaCO3(limestone). What is the percentage yield of calcium oxide?

The equation for the reaction involved is:

CaCO3(s) → CaO(s) + CO2(g)

From the equation, 1 mole CaCO3 → 1 mole CaO

[40.1 + 12 + (3 × 16)] g CaCO3 → (40.1 + 16) g CaO

So 100.1 g CaCO3 → 56.1 g CaO

Thus 1 g CaCO3 → 56.1/ 100.1 g CaO

Theoretical yield from 1000 kg CaCO3 = 56.1/ 100.1 × 1000 kg CaO = 560 kg

The actual yield of CaO = 500 kg CaO Percentage yield

= 500 kg / 560 kg × 100 = 89%

Atom economy

Atom economy = Example molar mass of the desired product / sum of the molar masses of all
the products × 100%

Titanium is manufactured by heating titanium(iv) chloride with magnesium. The equation for
the reaction at 1200 °C is:

TiCl4(g) + 2Mg(l) → Ti(s) + 2MgCl2(l)

What is the atom economy of this process?

Molar mass of all products = M(Ti) + 2M(MgCl2)

= 47.9 g mol−1 + 190.6 g mol−1 = 238.5 g mol−1

Molar mass of desired product = 47.9 g mol−1

Therefore: atom economy = 47.9 ÷ 238.5 × 100% = 20.1%

1.9 Define Avogadro’s constant.

1.10
A mole of atoms contains an enormous number of atom 6.02 × 1023 atoms. The Avogadro
constant, also known as the Avogadro number, is this value. The Avogadro constant’s symbol is
L (the symbol NA may also be used).

The Avogadro constant holds true for electrons, ions, molecules, and atoms. Thus, 6.02 × 1023
sodium atoms and 6.02 × 1023 sodium ions and chloride ions are present in 1 mole of sodium
chloride (NaCl) and 1 mole of sodium, respectively.

1.9 Use of Avogadro’s constant to calculate the mass of individual atoms/molecules.

What mass of sodium hydroxide, NaOH, is present in 0.25 mol of sodium hydroxide? (Ar values:
H = 1.0, Na = 23.0, O = 16.0)

Molar mass of NaOH = 23.0 + 16.0 + 1.0 = 40.0 g mol–1

Mass = number of moles × molar mass

= 0.25 × 40.0 g

= 10.0 g NaOH

1.11 Use of pV = nRT (the ideal gas equation) in calculations.

1.12
Calculate the volume occupied by 0.500 mol of carbon dioxide at a pressure of 150 kPa and a
temperature of 19 °C.

(R = 8.31 J K −1 mol−1)

Step 1 Change pressure and temperature to their correct units:

150 kPa = 150 000 Pa; 19 °C = 19 + 273 = 292 K

Step 2 Rearrange the general gas equation to the form you require:

pV = nRT so V = nRT / p
Step3 Substitute the fi gures: V = nRT / p

= 0.500 × 8.31 ×292 / 150000

= 8.09 × 10−3 m3

= 8.09 dm3

2.1 Prepare a solution of accurate concentration of an acid or base.

2.3 Use a burette to measure an accurate volume.

The following process is used to prepare a solution.

• Take a little known-concentration acid.

• After washing the burette with a little acid, fill a clean burette with the acid.

• Note the burette’s initial reading.

• Using a graduated (volumetric) pipette, measure a known volume of the alkali into a titration
flask.

• Fill the flask with the alkali and add an indicator solution. • Fill the flask gradually with the
acid from the burette, swirling it constantly until the indicator changes colour (the end-point).

2.2 Experiment to establish the end point of an acid-base reaction

• Take note of the final burette measurement. The titre is the final reading less the initial
reading. Typically, this first titre is referred to as a “rough” value.

• Continue in this manner, adding acid one drop at a time closer to the finish line.

• Continue until you have two titres that are separated by no more than 0.10 cm3.

• Compute these two titre values and take the mean.

Your findings ought to be listed in a table that resembles this one:

It is important to note that:

Rough 1 2 3

Final burette reading/cm3 37.60 38.65 36.40 34.75

Initial burette reading /cm3 2.40 4.00 1.40 0.00

Titre /cm3 35.20 34.65 35.00 34.75

• all burette readings are provided with an accuracy of 0.05 cm3;

• units are displayed as “/ cm3”;

• the two titres, 1 and 3, that are separated by no more than 0.10 cm3 will be averaged; and

• the average titre is 34.70 cm3.

Five key pieces of information are present in every titration:

1 The reaction’s balanced equation

2 The volume of the burette’s solution (hydrochloric acid in the example above).
3
4 The solution’s concentration within the burette
5
4 The volume of the solution (sodium hydroxide in the example above) in the titration flask.

6 The solution’s concentration within the titration flask. We can compute the fifth of these five
variables if we know the first four. We therefore need to be aware of the first four of these
points in order to compute the concentration of sodium hydroxide in the flask.
7
2.4 Calculation of an unknown quantity such as concentration of an acid or base using data from
the titration experiment.

Figure: a A funnel is used to fill the burette with hydrochloric acid. B A graduated pipette is used
to measure 25.0cm3 of sodium hydroxide solution into a conical flask. C An indicator called
litmus is added to the sodium hydroxide solution, which turns blue. D 12.5 cm3 of hydrochloric
acid from the burette have been added to the 25.0 cm3 of alkali in the conical flask. The litmus
has gone red, showing that this volume of acid was just enough to neutralise the alkali.

Titration-based solution concentration calculation:

To determine a solution’s precise concentration, a titration is frequently utilised. The

procedures for determining the concentration of a sodium hydroxide solution after it is
neutralised by aqueous sulfuric acid with a known concentration and volume are illustrated in
Worked Example below .

25.0 cm3 of a solution of sodium hydroxide is exactly neutralised by 15.10 cm3 of sulfuric acid
of concentration 0.200 mol dm−3.

2NaOH + H2SO4 → Na2SO4 + 2H2O

Calculate the concentration, in mol dm−3, of the sodium hydroxide solution.

Step 1 calculate the moles of acid moles

= concentration (mol dm−3) × volume of solution (dm3)

0.200 × 15.10 / 1000 = 0.00302 mol H2SO4

Step 2 use the stoichiometry of the balanced equation to calculate the moles of NaOH moles of
NaOH = moles of acid (from step 1) × 2 0.00302 × 2 = 0.00604 mol NaOH

Step 3 calculate the concentration of NaOH

Concentration (mol dm-3)

= number of moles of solute (mol)/volume of solution (dm )

= 0.006 04 / 0.0250

= 0.242 mol dm−3

Note 1 In the fi rst step we use the reagent for which the concentration and volume are both
known.

Note 2 In step 2, we multiply by 2 because the balanced equation shows that 2 mol of NaOH
react with every 1 mol of H2SO4 .

Note 3 In step 3, we divide by 0.0250 because we have changed cm3 to dm3 (0.0250 = 25.0 /
1000).

Note 4 The answer is given to 3 signifi cant figures because the smallest number of signifi cant
figures in the data is 3.

3 Bonding
1.1 Ionic bond
An ionic connection is created by the strong attraction between the positively and negatively
charged ions. Sometimes, an ionic link is referred to as an electrovalent bond.
When an atom gains or loses an electron, ions are created.
● When an atom loses one or more electrons, positive ions are created. Positive ions are
created when metal atoms lose electrons, whereas negative ions are created when an
atom contains one or more electrons.
● Typically, non-metal atoms pick up electrons to create negative ions. The amount of
electrons acquired or lost determines the charge of the ion. The electrons in the metal
atoms' outer shell are transferred to the non-metal atoms when metals mix with non-
metals. Normally, enough electrons are added to each non-metal atom to complete its
 outer shell. Because of this, the outer electron shells of both metal and non-metal atoms
are typically full.
1.2 Dot-and-cross diagrams for ionic compounds e.g. NaCl, MgCl2
Dot-and-cross diagram
Drawing the outer electron shell of a metal ion without any electrons is often acceptable when
creating a dot-and-cross diagram for an ionic combination. This is as a result of these electrons
being transferred to the negative ion.
A dot-and-cross diagram, represented by square brackets, indicates that the ion's charge is
distributed uniformly and only the outer electron shells. Each ion's charge, which is indicated at
the upper right corner of the square brackets.
NaCl

MgCl2

1.3 Formulae of ionic compounds by using criss-cross method including those containing
the group ions:
NH4+
NH4+1 ⤩ Cl-1
NH4Cl
CO32-
Mg+2 ⤩ CO3-2
MgCO3
OH-
Na+ ⤩ OH-
NaOH
NO3-
Ca+2 ⤩ NO3-
Ca(NO3)2
SO4 2-
Fe+3 ⤩ SO4-2
Fe2(SO4)3
1.4 Covalent bond
One or more pairs of electrons are shared when two non-metal atoms come together. A single
covalent bond, also known as a bond pair, is defined as a shared pair of electrons. A single line
connecting the atoms represents a single covalent bond.
Certain atoms can form bonds by exchanging two electron pairs. It is referred to as a double
covalent bond. A double line between the atoms indicates a double covalent bond.
Atoms can also bond together by sharing three pairs of electrons. We call this a triple covalent
bond.
The pairs of outer-shell electrons not used in bonding are called lone pairs.
When sketching the arrangement of electrons in a molecule, we can:
• utilize additional symbols, such as a small circle or triangle, if there are more than two types of
atoms; otherwise, we can use a "dot" for the electrons from one atom and a "cross" for the
electrons from the other atom.
• To highlight the quantity of bond pairs and lone pairs, we depict the outer electrons in pairs.
Several illustrations of dot-and-cross diagrams for basic molecules with covalent bonds.
1.5 Dot-and-cross diagrams for covalent compounds such as CH4, NH3, H2O, O2, N2, CO2,
ethane etc.

CH4
NH3

H2O

O2

N2
CO2

Ethane

1.6 Dative covalent bond.

When one atom supplies both of the electrons required for a covalent bond, a bond is created
which is called dative covalent bond also known as co-ordinate covalent bond.
A lone pair of electrons in one atom and an unfilled orbital in the second atom, or an electron-
deficient compound, are required for dative covalent bonding.
In a displayed formula (which shows all atoms and bonds), a co-ordinate bond is represented by
an arrow. The head of the arrow points away from the lone pair which forms the bond.
1.7 Dot-and-cross diagrams for covalent compounds that have dative covalent bonds such
as NH4+and H3O+.
NH4+
Ammonia and a hydrogen ion, H+, combine to form the ammonium ion, NH 4+. The shell of the
hydrogen ion can accommodate two electrons because it is electron-deficient. In the ammonia
molecule, the nitrogen atom possesses a single pair of electrons. Both electrons for the bond are
provided by the lone pair on the nitrogen atom.

H3O+

When an acid is added to water oxoniumion can form(H3O+)

1.8 Formation of a dative covalent bond e.g., the formation of Al2Cl6 and NH3BF3.
Al2Cl6
AlCl3 molecules, or aluminum chloride, are present at high temperatures.
This molecule is electron deficient; the aluminum atom's outer shell still needs two electrons to
be completed. Two molecules of AlCl3 combine to form a molecule with the formula Al2Cl6at
lower temperatures.
Because lone pairs of electrons on two of the chlorine atoms form coordinate bonds with the
aluminum atoms, the AlCl3 molecules can combine.

NH3BF3
The combination of gaseous ammonia and gaseous boron trifluoride forms NH 3BF3, a white
solid. In ammonia, the nitrogen atom possesses a lone pair, while in boron trifluoride, the boron
atom possesses an empty 2p [Link] nitrogen’s lone pair can overlap with this empty
orbitalThe nitrogen’s lone pair can overlap with this empty orbital.

1.9 Realtion between covalent bond strength and length.

Double bonds are typically shorter than single bonds. This is due to the fact that double bonds
have more negative charge between their two atomic nuclei. The atoms are drawn closer
together by the stronger attraction between the nuclei and electrons. This makes the bond
stronger. A bond's strength is determined by its bond energy. This is the amount of energy
required to break a single bond in a gaseous molecule.
Bond strength has an impact on a compound's reactivity. Because the molecules in liquids and
gases move randomly, they collide with one another all the time. Molecules can only react with
one another when they collide with sufficient energy to break bonds in one or both of the
molecules. Because nitrogen contains the triple bond N-N, it is not reactive. The bond energy
required to split nitrogen atoms is 994 kJ/mol. This is very high energy. Much more reactive is
oxygen. A mole of O-O bonds can be broken with 496 kJ despite its double bond. Bond strength,
however, is not the only element that affects a material's reactivity. The polarity of the bond and
whether the bond is a σ bond (sigma bond) or a π bond (pi bond) both play a large part in
determining chemical reactivity.
1.10 ‘Non-polar’ and ‘polar’ bonds for any given covalent bond.
Polar bonds
Bonds between atoms of different elements are called polar covalent [Link] atom that has a
greater pull on its electrons is the target of the shared electrons. One end of the bonds is
positively polarized, and the other is negatively polarized. The polar covalent bond has some
separation of charge.

Non polar bond

The pair of electrons is equally shared when the electronegativity values of the two atoms
forming the covalent bond are the same. The covalent bond is referred to as non-polar. Non-
polar molecules include hydrogen (H2), chlorine (Cl2), and bromine (Br2). The more
electronegative atom pulls the bond's pair of electrons toward it when two atoms with different
electronegativity values form a covalent bond.

1.11 Use of the term ‘dipole’ for any given covalent bond and assign partial charges to the
atoms in a covalent molecule
When a covalent bond is formed between two atoms having diff erent electronegativity values,
the more electronegative atom attracts the pair of electrons in the bond towards it. As a result:
The positive and negative charge centers are not at the same location. The two atoms are
partially charged. We demonstrate that the less electronegative atom with the partial charge δ+
(also known as "delta positive") is followed by the more electronegative atom with the partial
charge δ− (also known as "delta negative"). We also state that the bond is polar, or that it has a
dipole.
A covalent bond becomes more polar when the atoms' differences in electronegativity values
rise. A molecule's degree of polarity is expressed as a dipole moment.t. The direction of the
dipole is shown by the arrow points to the partially negatively charged end of the dipole.
1.12 Electronegativity.
An atom's ability to draw electrons from a covalent bond to itself is measured by its
electronegativity.
Numerous scientists have created quantitative electronegativity value scales. The scale
developed in 1960 by American chemist Linus Pauling is one of the most widely used. On this
scale, the numerical values of electronegativity range from 4.0 for fluorine to 0.9 for an alkali
metal like sodium.
1.13 Trend in electronegativity in the periodic table.
The atomic radius and effective nuclear charge determine the electronegativity value.
Ionization energies depend on both the atomic radius and the effective nuclear charge in a
manner similar to this, and for a similar reason. For example, the nucleus of a fluorine atom
(electronegativity value = 4.0) is able to attract electrons more strongly than that of a carbon
atom (electronegativity value = 2.5) because it has more protons and a higher effective nuclear
charge. Therefore, the electrons in the C-F bond will generally be found closer to fluorine than to
carbon. A polar bond will form as a result of a partial charge movement in the direction of the
fluorine atom.
The elements' electronegativity values listed in the periodic table's first three rows. Observe
that the atom is more electronegative (electron attracting) the higher the number.

As one moves down a particular group in the periodic table, the outermost (valence) electrons
are somewhat protected from the increased nuclear charge by the filled inner orbitals; however,
because they are moving away from the nucleus, they are subject to less nuclear attraction,
which causes electronegativity to decrease.
2.1 Finding the shape of an unfamiliar molecule
The number of lone pairs and bonding pairs of electrons on the central atom are
necessary to determine the shape of a molecule or an ion.
You only need to take the following actions to find out:
1. Find the central atom, it’s the one all the other atoms are bonded to.
2. Work out how many electrons are in the outer shell of the central atom. This will be the same
as its group number in the periodic table.
3. Add 1 electron for every atom that the central atom is bonded to. (You can work this out from
the formula of the molecule or ion.)
4. If you’re looking at an ion, you need to take its charge into account: add 1 electron for each
negative charge or subtract 1 for each positive charge.
5. Add up all the electrons. Divide by 2 to find the number of electron pairs.
6. Compare the number of electron pairs to the number of bonds to find the number of lone
pairs and the number of bonding pairs on the central atom.
Predict the shape of the BF4 – ion.
First follow the above mentioned steps after that:
1. The central atom is boron.
2. Boron is in Group 3, so it has 3 electrons in its outer shell.
3. The boron atom is bonded to 4 fluorine atoms.
4. BF3 is an ion with a 1– charge, so you need to add one extra electron to account for that. 5.
That means there are 3 + 4 + 1 = 8 electrons in the outer shell of the central boron atom. That’s 8
÷ 2 = 4 pairs.
6. The boron atom has 4 electron pairs around it, and has made 4 bonds. So it has 4 bonding
pairs and no lone pairs.
A molecule with 4 bonding pairs and no lone pairs will have a tetrahedral shape, with bond
angles of 109.5°. Now all you have to do is draw it.
3.1 Non-polar molecules in terms of molecular shape and dipoles.
In order for a molecule to be considered polar, it must have polar bonds; however, if these
bonds are sufficiently symmetric or oriented in the exact opposite direction of one another,
their polarities cancel out, rendering the molecule nonpolar.
Take the Lewis dot structure for carbon dioxide, for instance. This molecule is linear and has
two polar double bonds between carbon and oxygen. The molecule is nonpolar, though, because
the polar bonds are precisely 180° apart, canceling out the bond polarities.
3.2 Comparision between the intermolecular forces such as: van der Waals, permanent
dipole-dipole and hydrogen bonding.
Van der waals’ forces
The intermolecular forces that exist between every molecule are known as van der waal’s
forces.
They are the result of the attraction between transient instantaneous dipoles and the transient
dipoles they cause in molecules that are nearby.
The van der Waals forces rise as the molecule's electron and proton counts rise. Increasing the
quantity of molecular contact points, or locations where molecules are in close proximity to one
another. The trend in the enthalpy change of vaporization and boiling points of the noble gases
can be explained by variations in the magnitude of the van der Waals forces. As the number of
electrons increases, so do the noble gas boiling points and the enthalpy change of vaporization.
This is due to the fact that as the number of electrons increases, so do the van der Waals forces
between the atoms. Consequently, the boiling point is higher and more energy is required to
turn the liquid into vapor. Comparing the boiling points reveals the effect of increasing the
number of contact points.
Permanent dipole-dipole
The forces between two molecules having permanent dipoles are called permanent dipole–
dipole forces.
A weak attractive force exists between molecules due to the attraction between the partial
positive charge on one and the partial negative charge on a nearby molecule.
Permanent dipole–dipole forces are frequently stronger than van der Waals forces for small
molecules with the same number of electrons. For example propanone has a higher boiling
point than butane. This indicates that the intermolecular forces between propanone molecules
must be broken with more energy than those between butane molecules.

Propanone is a liquid at room temperature due to the strong dipole–dipole forces that exist
between its molecules. The only forces that exist between butane molecules are van der Waals
forces. Because of how weak these forces are, butane is a gas at room temperature.
Hydrogen bonding
The strongest kind of intermolecular force is hydrogen bonding. In order for two molecules to
form a hydrogen bond, one of the molecules must have a hydrogen atom covalently bound to the
greatest number of electronegative atoms and the second molecule having an available lone pair
of electrons.
A very highly polarized bond forms when a hydrogen atom covalently bonds with an extremely
electronegative atom. A bond can be formed between the hydrogen atom's δ+ charge and a lone
pair of electrons on the F, O, or N atom of a neighboring molecule. About one-tenth of the
strength of a typical covalent bond makes up the force of attraction. The angle formed by the
hydrogen bond and the covalent bond to the hydrogen atom is typically 180° for maximum
bond strength.

3.3 The origin of van der Waals forces in terms of the random movement of electrons.
To explain why actual gases behave as they do, the Dutch physicist Johannes van der Waals
(1837–1923) created the theory of intermolecular forces. It would not be possible to cool a gas
into a liquid if there were no molecular attractions. Certain gases have weak attraction forces
that prevent them from liquefying until extremely low temperatures are attained.
The intermolecular forces that exist between all molecules. They arise from the attractions
between temporary instantaneous dipoles and the fleeting dipoles they induce in neighbouring
molecules are called van der waals forces.
A non-polar molecule (or atom's) electron charge clouds are in constant motion. One side of the
molecule frequently has a larger concentration of the charge cloud than the other. This indicates
that for a brief period of time, one end of the molecule has a greater negative charge than the
other. A makeshift dipole is installed. This dipole has the ability to create (induce) a dipole on
nearby molecules. The δ+ end of a dipole in one molecule and the δ− end of a dipole in a
neighboring molecule are therefore attracted to each other.
These dipoles are ephemeral due to the constant motion of the electron clouds. Temporary
dipole-induced dipole forces is another term for Van der Waals' forces.

3.4 Hydrogen bonding in molecules such as NH3 and H2O.

Hydroegn bonding in H2O

Hydrogen bonding in NH3

3.5 The reasion of low boiling points in some molecules such as CH4 and Br2.
Among the compounds, methane (CH4) has the lowest boiling point due to its weaker London
dispersion forces. Since CH4 has fewer electrons than the other compounds, it has weaker
London dispersion forces.
Bromine molecules (Br2) are diatomic and are only held together by weak van der Waals forces.
Because of these variations in intermolecular forces, water boils at a higher temperature than
bromine.
3.6 Trend in boiling point of group 6 hydrides and group 7 hydrogen halides.
It is evident from a comparison of the boiling points of Group 6 hydrides that the boiling point of
water is much higher than predicted. The strength of the London forces between molecules
increases as we move down the group and increase the number of electrons, increasing the
boiling point.

The melting and boiling points rise as one moves down group 7. The intermolecular forces
intensify as the atoms grow larger due to the addition of additional electron shells. Lower on the
group, melting and boiling points are higher because it takes more energy to break these forces.
Covalent bonds bind halogens together.
3.7 Explain the solubility of simple covalent compounds in different solvents.
Solubility is a measure of the concentration of a saturated solution of a solute at a specified
temperature. Solubilities are commonly recorded as ‘mol per 100g water’ or ‘g per 100g water’
at 25°C (298K).
Solubility of covalent compounds is limited to non-polar solvents. However, water has charge
separation, making it a polar solvent. However, the majority of organic solvents lack polarity.
There are two classes of covalently bonded materials with basic molecular structures.
• The ones that are water insoluble. Most molecules with covalent bonds are non-polar. They
are soluble because the molecules of water are not drawn to them. Take iodine as an example.
• The ones that are water insoluble. In general, small molecules that have the ability to form
hydrogen bonds with water are soluble. C2H5OH, or ethanol, is one example. Certain materials
with covalent bonds react with water instead of dissolving in it. For instance, when hydrogen
chloride and water react, the ions that result are soluble and include both hydrogen and
chloride ions. Hydrogen ions, chloride ions, and silicon dioxide are produced when silicon
chloride and water react. This process is known as a hydrolysis reaction.
4.1 Unusual properties of water, including its boiling point in relation to other Group 6
hydrides and it being less dense in the solid state.
Water should have an enthalpy change of roughly 17 kJ/mol if the only forces interacting with
its molecules were van der Waals forces. However, the water vaporization process has a much
larger enthalpy change. This is a result of the extensive hydrogen bonding in water. The trend in
boiling points for the other Group VI hydrides does not match the boiling point of water, which
is likewise much higher. This suggests that compared to other Group VI element hydroides, a lot
more energy is needed to break the bonds separating water molecules.
Both surface tension and viscosity are high in water. Because hydrogen bonds make it harder
for water molecules to slide past one another, water has a high viscosity. At the liquid's surface,
the hydrogen bonds in water also significantly push downward. Because of this, water has a
higher surface tension than most other liquids.
4.2 Metallic bonding.
The positive metal ions are attracted to the delocalised negative electrons. They form a lattice of
closely packed positive ions in a sea of delocalised electrons; this is metallic bonding.
4.3 Sketch simple diagrams to represent metallic bonding.

4.4 Metals are good conductors of heat and electricity.

Excellent heat conductors: as a metal heats up, energy is transferred to the electrons. Heat
(energy) is rapidly conducted to other parts of the metal by the delocalized electrons in the
heated region, which travel around more quickly.
Good conductors of electricity: Delocalized electrons are drawn to the positive electrode and
flow through metals when a potential difference is applied across them. An electric current is
this electron flow.
4.5 Trend in melting point of metals across period 3.
Elevated melting and boiling points is due to strongly held forces between delocalized electrons
and positive ions, metal atoms are densely packed. Thus, a great deal of energy is required to
shift the positive ions' locations within the massive lattice, enabling the melting of the metal. At
the boiling point, it requires even more energy to separate individual atoms in the metal.

4.6 Identification of ionic, metallic and covalent compounds from chemical formulae.
Generally speaking, compounds involving a metal binding with a semi-metal or non-metal will
exhibit ionic bonding. Molecular compounds are defined as compounds that contain only non-
metals or semi-metals along with non-metals and exhibit covalent bonding. Hence, the
combination of sodium and chlorine will be ionic, meaning it will consist of a metal and a non-
metal. Two non-metals will be covalently bound to form nitrogen monoxide (NO), two semi-
metals and a non-metal will form covalently bound silicon dioxide (SiO 2), and two metals and a
non-metal will form an ionic compound in magnesium chloride (MgCl2).
4.7 Classification of ionic, metallic and macromolecular (giant covalent)
molecules/compounds as giant lattice structures.
Ionic lattices
Positive and negative ions are arranged in three dimensions in ionic lattices. Ionic lattice
compounds are also referred to as giant ionic structures. The relative sizes of the ions present
determine the kind of lattice that forms. Magnesium oxide and sodium chloride have cubic ionic
lattices. Six oppositely charged chloride ions encircle each sodium ion in sodium chloride. The
sodium ions are substantially smaller than the chloride ions. To get as close to the chloride ions
as possible, the sodium ions fit into the gaps between them.
Metallic lattices
Ions are encircled by a sea of electrons in a metallic lattice. The ions are frequently arranged in
cubic or hexagonal layers.
The layers can slide over one another in response to an applied force. However, in a metallic
bond, the delocalized electrons and the metal ions are attracted to each other in all directions.
Therefore, new metallic bonds between ions in new lattice positions and the delocalized
electrons are easily formed when the layers slide.
The ions in the lattice are still held together by the delocalized electrons. The metal is now
shaped differently. This explains why metals are ductile; they can be pulled into wires and
malleable; they can be hammered into a variety of shapes. Strong attractive forces between the
metal ions and the delocalized electrons are another factor contributing to the high tensile
strength and hardness of most metals.

A few non-metal elements, such as silicon and carbon, are made up of enormous atom
structures bound together by covalent bonds.
Giant covalent structures
Certain non-metal compounds, like boron nitride and silicon dioxide, can also exist as enormous
covalent structures. Giant covalent substances have extremely high melting temperatures and
are extremely hard due to the strong covalent bonds found in these structures.
There are several solid forms of carbon, including graphene, diamond, graphite, and different
fullerenes. Allotropes are distinct forms of the same element in the same physical state, such as
the solid forms of carbon.
These carbon forms serve as important examples of the relationships that exist between a
material's structure and bonding, its properties, and ultimately its applications.
Covalent bonds of a specific length and direction bind all of these forms of carbon together. In
contrast to fullerenes, which are comparatively simple molecules, diamond, graphite, and
graphene are enormous covalent structures.
4.8 Comparision between the macromolecular structures of graphite, diamond, silicon
(IV) oxide and graphene.
Structure of graphite:
Structure of dimond:

Structure of silicon (iv) oxide:

Structure of Graphene:
4.9 The melting point, conductivities and uses of macromolecular structures.
A three-dimensional web of covalent bonds permeates the entirety of some covalently bonded
structures. These structures are referred to as giant covalent or giant molecular structures.
Their high melting and boiling points can be attributed to the numerous strong covalent bonds
that bind the entire structure together. Massive molecular structures can be found in both
compounds, like silicon dioxide, and elements, like carbon (graphite and diamond). The element
carbon exists in two different forms: graphite and carbon. Allotropes are distinct crystalline or
molecular forms of the same element.

4 Enthalpy and Entropy

1.1 Enthalpy change
The energy exchange that occurs at constant pressure between a chemical reaction and its
environment is referred to as the enthalpy change. The total energy connected to the reacting
materials is called enthalpy. The letter H stands for enthalpy. Enthalpy itself cannot be
measured, but it can be measured when heat energy is exchanged with the environment.
∆H = Hproducts - Hreactants
The symbol ∆ is the uppercase Greek letter ‘delta’. This symbol is often used to mean a change in
a quantity.
1.2 Standard conditions
The same conditions in every enthalpy change comparison in order to ensure fairness. These
are referred to as typical circumstances:
• 105 Pa of pressure, or roughly 100 kPa, the standard atmospheric pressure.
• a temperature of 298 K, or 25 °C (to convert a temperature from Celsius to Kelvin, add 273)
• At 105 Pa and 298 K, every substance engaged in the reaction is in its typical physical state,
whether it be a solid, liquid, or gas.
The symbol ϴ denotes that a reaction conducted under standard conditions is the one to which
the enthalpy change relates.
1.3 Exothermic and endothermic
Exothermic reactions are those in which energy is released into the environment when a bond
breaks. The ambient temperature rises during an exothermic reaction. For instance, the energy
released during the reaction of magnesium and sulfuric acid in a test tube is transferred to the
surrounding environment, raising the reaction mixture's temperature in the tube.
Endothermic chemical reactions are those that take in energy from their surroundingswhen
bonds are formed. The ambient temperature drops during an endothermic reaction. For
instance, the temperature of the reaction mixture in a test tube drops when sodium
hydrogencarbonate reacts with an aqueous solution of citric acid. The heat energy from the
solvent, the test tube, and the air is being absorbed by the sodium hydrogen carbonate and citric
acid.
1.4 Reaction profile diagrams labelling for exothermic and endothermic reactions.
To illustrate enthalpy changes, we can create enthalpy profile diagrams, also referred to as
reaction pathway diagrams.
On the y-axis is the enthalpy of the reactants and products. The reaction pathway is depicted on
the x-axis, where products are on the right and reactants are on the left.
An exothermic reaction releases energy into the environment. As a result, the reactants'
enthalpy must be higher than the products' enthalpy. We can see from the enthalpy profile
diagram for the combustion of methane (Figure below) that Hproducts - Hreactants are negative.

We can include this information in the equation for the reaction:

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = −890.3 kJ mol-1
The negative sign shows that the reaction is exothermic.
In an endothermic reaction, the reacting chemicals take in energy from their environment. Thus,
the products' enthalpy needs to be higher than the reactants' enthalpy.
We can see from the enthalpy profile diagram for the thermal decomposition of calcium
carbonate (Figure below) that Hproducts - Hreactants are positive.
CaCO3(s) → CaO(s) + CO2(g) ∆H = +572 kJ mol-1
The positive sign shows that the reaction is endothermic.

1.5 Mean (average) bond enthalpy

The amount of energy needed to break a specific covalent bond is called the bond dissociation
energy. We sometimes call this the bond energy or bond enthalpy. The symbol for bond energy
is E.
Other atoms within the molecule have an impact on the bond energy.
The O-H bond in ethanol is slightly different from the O-H bond in water because in ethanol, the
oxygen atom is linked to a carbon atom instead of another hydrogen atom. The surroundings of
the O-H bond are different. When we measure identical bonds in molecules containing two or
more different types of bonds, the bond energies differ. In water, breaking the first O-H bond
requires more energy than breaking the second.
We utilize average bond energies derived from multiple bonds of the same type in various
environments for these reasons.
1.6 Calculation of the enthalpy change of a reaction using mean bond enthalpy data
We can use bond enthalpies to calculate the enthalpy change of a reaction that we cannot
measure directly.
For example, the reaction:
N2(g) + 3H2(g) ⇋ 2NH3(g)
The enthalpy cycle for this reaction is shown in Figure below . The relevant bond energies are:
E(N≡ N) = 945 kJ/mol
E(H─H) = 436 kJ/mol
E(N⎼H) = 391 kJ/mol
It is often easier to set out the calculation as a balance sheet, as shown below.

Notice in these calculations that:

• one triple bond in nitrogen is broken
• three single bonds in hydrogen are broken
• six single N-H bonds in hydrogen are formed (because each of the two ammonia molecules has
3 N-H bonds)
• values for bond breaking are positive since these are endothermic and values for bond
forming are negative since these are exothermic.
From the enthalpy cycle:
∆Hr = ∆H1 + ∆H2
∆Hr = enthalpy change for bonds broken + enthalpy change for bonds formed
∆Hr = 2253 + (−2346) = −93 kJ/mol
1.7 Calculation of a mean bond enthalpy using mean bond enthalpy data and the enthalpy
change of a reaction
Typically, it is not possible to determine mean bond enthalpy directly, thus an enthalpy cycle
must be utilized. The enthalpy changes of carbon and hydrogen atomization as well as the
enthalpy change of methane formation or combustion can be used to determine the average
bond energy of the C–H bond in methane.
The figure below illustrates the enthalpy cycle used to determine the average C-H bond energy.

Using the enthalpy cycle, the average C H bond energy can be found by dividing the value of ∆H
on the diagram by four (because there are four C H bonds in a molecule of methane).
1.8 The reasons for differences in enthalpy changes of calculated and literature values
when using mean bond enthalpies.
The values of enthalpy obtained experimentally are frequently far from the values computed
using the bond enthalpy terms. This is because the values are averages and do not account for
scenarios where the bond strength deviates from the average. Among the potential reasons for
variation are: the effect of induction.
1.9 Define the following terms:
i.) enthalpy of combustion
The standard enthalpy change of combustion is the enthalpy change when one mole of a
substance is burnt in excess oxygen under standard conditions. The reactants and products
must be in their standard states.
The symbol for standard enthalpy change of combustion is ∆H ϴc . Enthalpy changes of
combustion are always exothermic.
ii.) enthalpy of formation
The standard enthalpy change of formation is the enthalpy change when one mole of a
compound is formed from its elements under standard conditions. The reactants and products
must be in their standard states.
The symbol for standard enthalpy change of formation is ∆Hϴf . Enthalpy changes of formation
can be exothermic or endothermic.
iii.) enthalpy of neutralisation
The standard enthalpy change of neutralisation is the enthalpy change when one mole of water
is formed by the reaction of an acid with an alkali under standard conditions.
The symbol for standard enthalpy change of formation is ∆Hϴn .
1.10 Construction of enthalpy cycles using Hess’s law based on enthalpies of combustion
and formation
Hess’s law states that ‘the total enthalpy change in a chemical reaction is independent of the
route by which the chemical reaction takes place as long as the initial and final conditions are
the same’.
Enthalpy change of formation from enthalpy changes of combustion
Using the kind of enthalpy cycle depicted in the following figure, we can determine the enthalpy
change of formation for a wide variety of compounds.
To determine the enthalpy change of formation, we utilize the enthalpy changes of combustion
of the reactants and products. Using Hess's law and noting the direction of the arrows to
identify the direct and indirect one- and two-stage routes, we can observe that
∆H1 = ∆Hf + ∆H2
direct route indirect route
So ∆Hf = ∆H1 − ∆H2

With this kind of cycle, the enthalpy change of formation is calculated as follows:
• To balance the combustion reactions, write the enthalpy change of formation equation at the
top and add oxygen on both sides.
• illustrate the cycle, with the combustion products at the bottom;
• ensure that all of the arrows point in the right directions.
• Utilize Hess's law, accounting for the moles of every reactant and product.
1.11 Calculation of enthalpy changes using Hess cycles
Calculate the standard enthalpy change of formation of ethane, C2H 6. The relevant enthalpy
changes of combustion are:
C(graphite) + O2(g) → CO2(g) ∆Hc [C(graphite)] = −393.5 kJ mol−1
H2(g) + ½ O2(g) → H2O(l) ∆Hc [H2(g)] = −285.8 kJ mol−1
C2H6(g) + 3.½ O2(g) → 2CO2(g) + 3H2O(l) ∆Hc [C2H6(g)] = −1559.7 kJ mol−1
The enthalpy cycle is shown in Figure below:

The enthalpy cycle to find the enthalpy change of formation of ethane using enthalpy changes of
combustion. The dashed line shows the two-step route.
Using Hess’s law
∆H1 = ∆Hf + ∆H2
2(−393.5) + 3(−285.8) = ∆Hf + (−1559.7)
−1644.4 = ∆Hf + (−1559.7)
So ∆Hf = −1644.4 − (−1559.7) = −84.7 kJ mol−1
1.12 Define the following terms:
i.) lattice enthalpy
Lattice energy is the enthalpy change when 1 mole of an ionic compound is formed from its
gaseous ions under standard conditions.
ii.) atomisation enthalpy
The standard atomisation enthalpy, is the enthalpy change when 1 mole of gaseous atoms is
formed from its element under standard conditions.
iii.) electron affinity
The electron affinity is the enthalpy change when 1 mole of electrons is added to 1 mole of
gaseous atoms to form 1 mole of gaseous 1– ions under standard conditions.
1.13 Enthalpy changes in Born-Haber cycles of ionic compounds
A Born–Haber cycle is a particular type of enthalpy cycle used to calculate lattice energy. In
simple terms it can be represented by Figure below:
We can determine the lattice energy of a compound if we know:
■ its enthalpy change of formation, ΔHf
■ the enthalpy changes involved in changing the elements from their standard states to their
gaseous ions, ΔH1
According to Hess’s law, Figure shows that:
ΔH1 + ΔHlatt = ΔHf
Rearranging this equation we get:
ΔHlatt = ΔHf – ΔH1
The enthalpy change ΔH1 involves several steps.
1.14 Construction of Born-Haber cycles of ionic compounds.
Taking lithium fluoride as an example, the relevant enthalpy cycle can be written to show these
steps (Figure below)

1.15 Use of Born-Haber cycles to calculate various enthalpy changes

The enthalpy changes needed to calculate ΔH1 are as follows.
Step1 Convert solid lithium to gaseous lithium atoms:
The enthalpy change required is the enthalpy change of atomisation of lithium, ΔHat
Li(s) ⟶ Li(g) ΔHat = +161 kJ/mol
Step2 Convert gaseous lithium atoms to gaseous lithium ions:
The enthalpy change required is the 1st ionisation energy of lithium,ΔHi1.
Li(g) ⟶ Li+(g) + e– ΔHi1 = +520 kJ/mol
Step3 Convert fluorine molecules to fluorine atoms: the enthalpy change required is the
enthalpy change of atomisation of fluorine, ΔHat
½F2(g) ⟶ F(g) ΔHat = +79 kJ/mol
Step4 Convert gaseous fluorine atoms to gaseous fluoride ions: the enthalpy change required is
the 1st electron affinity of fluorine, ΔHea1
F(g) + e– ⟶ F–(g) ΔHea1 = –328 kJ/mol
Step5
By adding all these values together, we get a value for ΔH 1. The enthalpy change of formation of
lithium fluoride is –617 kJ/mol. We now have all the information we need to calculate the lattice
energy.
1.16 Relative lattice enthalpy values from chemical formulae of ionic compounds
Applying Hess’s law to find the lattice energy of lithium fluoride:
ΔHlatt = ΔHf – ΔH1
We know that:
ΔH1 = ΔHat [Li] + ΔHi1 [Li] + ΔHat [F] + ΔHea1 [F]
So
ΔHlatt = ΔHf – {ΔHat[Li] + ΔHi1[Li] + ΔHat[F] + ΔHea1[F]}
Putting in the figures:
ΔHlatt = (–617) – {(+161) + (+520) + (+79) + (–328)}
= +432
ΔHlatt = (–617) – (+432) = –1049 kJ/mol
Note: take care to account for the signs of the enthalpy changes. The values of the enthalpy
changes of formation and the electron affinity may be negative or positive.
1.17 Polarisation in relation to lattice enthalpies
We have assumed that the ions in our ionic lattice model are spherical in shape. Not all the time
is this the case. The electrons in the anion may occasionally be drawn to the cation due to its
positive charge in an ionic lattice. As a result, the anion's electron cloud becomes distorted and
it stops being spherical (Figure below).
This distortion is known as ion polarization. The term "polarising power" refers to a cation's
capacity to draw electrons and change an anion.

Factors affecting ion polarisation

The degree of polarisation of an anion depends on:
■ The charge density of the cation
■ The ease with which the anion can be polarised – its polarisability.
An anion is more likely to be polarised if:
■ The cation is small
■ The cation has a charge of 2+ or 3+
■ The anion is large
■ The anion has a charge of 2– or 3–.
Electrons can be drawn to a small, highly charged cation like Fe 3+, which can then distort a larger
anion to the point where a significant amount of covalent character is formed in the bond.
Extremes include pure covalent and pure ionic bonding. Ion polarization gives many ionic
compounds some covalent properties. Due to bond polarization, many covalent compounds
have some degree of charge separation, making them polar.
1.18 Comparision between the differences in experimental and theoretical lattice
enthalpies.
By performing some calculations using the purely ionic model of a lattice, you can determine the
theoretical lattice enthalpy. A lattice's purely ionic model postulates that each ion is spherical
and that their charges are dispersed equally around them. However, the Born-Haber cycle's
experimental lattice enthalpy is typically different. This demonstrates that ionic compounds
typically possess some covalent properties. Typically, a lattice's positive and negative ions
aren't perfectly spherical (see figure below). To varying degrees, positive ions polarize nearby
negative ions; the greater the polarization, the more covalent the bonding.

If the experimental and theoretical lattice enthalpies for a compound are very different, it shows
that the compound has a lot of covalent character.
If the experimental and theoretical lattice enthalpies for a compound are very similar, it shows
that the compound has very little covalent character.
1.19 Define the following terms:
i.) enthalpy of solution
The enthalpy change of solution, ∆Hsol, is the energy absorbed or released when 1 mole of an
ionic solid dissolves in sufficient water to form a very dilute solution.
ii.) enthalpy of hydration
The enthalpy change of hydration, ∆Hhyd, is the enthalpy change when 1 mole of a specified
gaseous ion dissolves in sufficient water to form a very dilute solution.
1.20 Predict relative enthalpy of hydration values from chemical formulae of ionic
compounds.
The enthalpy changes of hydration for calcium ions and chloride ions are described by the
equations below:
Ca2+(g) + aq → Ca2+(aq) ∆Hhyd = −1650 kJ/mol
Cl− (g) + aq → Cl− (aq) ∆Hhyd = −364kJ/mol
Note that:
• the symbol for enthalpy change of hydration is ∆Hhyd
• the enthalpy change of hydration is always exothermic
• the value of ∆Hhyd is more exothermic for ions with the same charge but smaller ionic radii, e.g.
∆Hhyd is more exothermic for Li+ than for Na+
• The value of ∆Hhyd is more exothermic for ions with the same radii but a larger charge e.g. ∆Hhyd
is more exothermic for Mg2+ than for Li+ .
1.21 Hess cycles and Born Haber cycles that show enthalpy of solution, enthalpy of
hydration and lattice enthalpy
We can calculate the enthalpy change of solution or the enthalpy change of hydration by
constructing an enthalpy cycle and using Hess’s law.
We can see from this enthalpy cycle that
∆Hlatt + ∆Hsol = ∆Hhyd
Note that the ∆Hhyd values for both anions and cations are added together to get the total value
of ∆Hhyd.
We can use this energy cycle to calculate:
• the value of ∆Hsol
• the value of ∆Hhyd.
1.22 Calculation of enthalpy of solution, enthalpy of hydration or lattice enthalpy from a
Hess or Born Haber cycle
Determine the enthalpy change of solution of sodium fluoride using the following data:
• lattice energy = −902 kJ/mol
• enthalpy change of hydration of sodium ions = −406 kJ/mol
• enthalpy change of hydration of fluoride ions = −506 kJ/mol
Step 1: draw the enthalpy cycle (Figure below)

Step2: rearrange the equation and substitute the figures to find ∆Hsol
∆Hlatt + ∆Hsol = ∆Hhyd
So
∆Hlatt + ∆Hsol = ∆Hhyd
∆Hsol = (−406) + (−506) − (−902)
= −912 + 902
∆Hsol [NaF] = −10 kJ/mol
1.23 The enthalpy of solution value indicates about the solubility of an ionic compound
Table below shows the solubility in water of some Group II sulfates. The solubility decreases as
the radius of the metal ion increases. We can explain this variation in solubility in terms of the
relative values of enthalpy change of hydration and the corresponding lattice energy.

Compound Solubility in mol dm−3

magnesium sulfate 1.83

 calcium sulfate 4.66 × 10−2

strontium sulfate 7.11 × 10−4

barium sulfate 9.43 × 10−6

The substances which have a very low solubility in water are likely to have ∆H sol with a high
positive (endothermic) value. As a rough guide, the higher the positive value of ∆H sol the less
soluble the salt.
• The lattice energy of the sulfates decreases (gets less exothermic) by relatively smaller values
down the group
• The enthalpy change of hydration decreases (gets less exothermic) by relatively larger values
down the group in the periodic table.
1.24 Entropy.
The measure of disorderiness is entropy. It is a measurement of the number of configurations
for particles and ways in which energy can be distributed among them. Particles move in an
attempt to increase entropy because substances have a strong affinity for disorder. An
illustration of entropy is the letter S.
∆S = Sproducts – Sreactants
A few factors that influence entropy are as follows:
Physical state
State of matter influences entropy. To understand this, you have to go back to the classic solid-
liquid-gas particle explanation. Solid particles have the lowest entropy because they essentially
have no disorder and just oscillate around a fixed point. Particles of gas swirl in any direction
they please. They have the highest entropy because their particle arrangements are the most
chaotic.

Dissolution
Dissolving a solid also increases its entropy dissolved particles can move freely as they’re no
longer held in one place:
Number of particles
More particles means more entropy. It makes sense the more particles you’ve got, the more
ways they and their energy can be arranged. So in a reaction like N2O4(g) ⟶ 2NO2(g), entropy
increases because the number of moles increases.

1.25 Entropy influence the solubility of an ionic compound

Reaction of NaHCO3 and HCl
When sodium hydrogen carbonate reacts with hydrochloric acid there is an increase in entropy.
NaHCO3(s) + H+ (aq) ⟶ Na+ (aq) + CO2(g) + H2O(l)

There are more particles in the products and gases and liquids have more entropy than solids
too.
1.26 The sign of the entropy change, ∆S, from chemical equations
Most reactions won’t happen unless the entropy change is positive. During a reaction, there’s an
entropy change (∆S) between the reactants and products.
This is just the difference between the entropies of the reactants and products.
∆S = Sproducts – Sreactants
S° is the standard entropy. The S° value of a substance is the entropy of one mole of that
substance, measured under standard conditions.
The unit of entropy is J K–1mol–1.
1.27 Calculation of entropy changes for reactions given standard entropy values
Calculate the entropy change for the reaction of ammonia and hydrogen chloride under
standard conditions.
NH3(g) + HCl(g) ➝ NH4Cl(s)
S° [NH3(g)] = 192.3 J K–1mol–1
S° [HCl(g)] = 186.8 J K–1mol–1
S° [NH4Cl(s)] = 94.6 J K–1mol–1
∆S = Sproducts – Sreactants
= 94.6 – (192.3 + 186.8)
= –284.5 J K–1mol–1
This reaction has a negative change in entropy. It’s not surprising, as 2 moles of gas have
combined to form 1 mole of solid.
1.28 Gibbs free energy
Free-energy change, ∆G, is a measure used to predict whether a reaction is feasible. A feasible
reaction is one that, once started, will carry on to completion, without any energy being
supplied to it. If ∆G is negative or equal to zero, then the reaction is feasible. Free-energy change
takes into account the changes in enthalpy and entropy in the system.
∆G = ∆H – T∆S
Where:
∆G= Free-energy change (in J/mol)
∆H= Enthalpy change (in J/mol)
∆S= Entropy change (in J K–1 mol–1)
T= Temperature (in K)
1.29 Calculation of ∆G using ∆G = ∆H - T∆S.
Calculate the free-energy change for the following reaction at 298 K.
MgCO3(s) ⟶ MgO(s) + CO2(g)
∆H° = +117 kJ/mol
∆S° = +175 J K–1 mol–1
∆G = ∆H – T∆S
= +117 × 103 – [298 × (+175)]
= +64 900 J/mol
∆G is positive, so the reaction isn’t feasible at this temperature.
1.30 Whether a reaction is feasible or not depends on the value of G.
Free-energy change, ∆G, is a measure used to predict whether a reaction is feasible. A feasible
reaction is one that, once started, will carry on to completion, without any energy being
supplied to it. If ∆G is negative or equal to zero, then the reaction is feasible. Free-energy change
takes into account the changes in enthalpy and entropy in the system.
A negative ∆G doesn’t guarantee a reaction will happen or tell you about its rate. Even if ∆G
shows that a reaction is theoretically feasible, it might have a really high activation energy or be
so slow that you wouldn’t notice it happening at all.
1.31 The effect of temperature on the feasibility of a reaction given enthalpy and entropy
values.
Given that ∆G = ∆H – T∆S, ∆G is always negative in the case of an exothermic reaction (negative
∆H) with a positive entropy change. Any temperature can cause these reactions to occur.
∆G is always positive in the event that a reaction is endothermic (positive ∆H) and experiences a
negative entropy change. It is not possible to have these reactions at any temperature. On the
other hand, temperature affects other combinations.
If ∆H is positive (endothermic) and ∆S is positive then the reaction will only be feasible above a
certain temperature.
If ∆H is negative (exothermic) and ∆S is negative then the reaction will only be feasible below a
certain temperature.
1.32 The role of kinetics in determining the feasibility of a reaction.
If ∆H is positive (endothermic) and ∆S is positive then the reaction will only be feasible above a
certain temperature.
Example :
The decomposition of calcium carbonate is endothermic but results in an increase in entropy
(the number of molecules increases and CO2 is a gas).
CaCO3(s) ⟶ CaO(s) + CO2(g)
The reaction only occurs when CaCO3 is heated it isn’t feasible at 298 K.
If ∆H is negative (exothermic) and ∆S is negative then the reaction will only be feasible below a
certain temperature.
Example :
The process of turning water from a liquid to a solid is exothermic but results in a decrease in
entropy (a solid is more ordered than a liquid). So it will only occur at certain temperatures (i.e.
at 0 °C or below).
When ∆G is zero, a reaction is just feasible. You can find the temperature when ∆G is zero by
rearranging the free-energy equation.
∆G = ∆H – T∆S, so
when ∆G = 0, T∆S = ∆H. So:
T = ∆H/∆S
1.33 Experiments to measure the heat change for reactions such as neutralisation and
combustion
To measure ΔHc (heat changes of combustion)
A simple apparatus
A basic device to measure the enthalpy change of combustion for a fuel like methanol is
depicted in the figure below. A copper calorimeter is used to measure the temperature of a
known volume of water. The fuel-containing spirit burner is clamped so that the calorimeter's
base is only a few centimeters above it. After being weighed, the spirit burner is set beneath the
calorimeter and lit. Using the thermometer, stir the water in the calorimeter. The flame is
extinguished, the temperature is recorded, and the spirit burner is weighed again once it has
increased by roughly 10°C.
Thiemann’s fuel calorimeter
When determining ΔHc using a copper calorimeter, there are two major sources of error:
The methanol is not all completely burnt to carbon dioxide and water (some incomplete
combustion takes place).
Not all the heat given off is passed to the water.
These errors can be reduced by means of Thiemann’s fuel calorimeter (see Figure below). The
fuel is burnt in a stream of oxygen to ensure complete combustion, and the gases are sucked
through a copper spiral placed in water (a heat exchanger) so that very little heat is lost to the
air.
Measurements similar to those with the simple copper calorimeter experiment are made. The
cap is replaced on the spirit burner after putting out the flame to reduce losses of fuel by
evaporation before re-weighing. The oxygen should be supplied fast enough so that the fuel
burns with a clear blue flame. The suction pump is usually fully on, but it may need to be turned
down if the suction is so vigorous that the flame is pulled off the spirit burner. Thiemann’s
apparatus can give results to within 80% of quoted values.
1.34 Plots of temperature versus time
A graph of free-energy (∆G) versus temperature (T), you can use it to work out the enthalpy
change (∆H) and entropy change (∆S) for the reaction.

1.35 Plots of temperature versus time to calculate accurate values for T

A graph being used to find the temperature change for a reaction beginning at time=2minutes.

1. During the experiment, record the temperature at regular intervals, beginning a couple of
minutes before you start the reaction.
2. Plot a graph of your results.
3. Draw two lines of best fit: one going through the points from before the reaction started and
one going through the points from after it started.
4. Extend both lines so that they both pass the time when the reaction started.
5. The distance between the two lines at the time the reaction started (before any heat was lost)
is the accurate temperature change ( ∆T) for the reaction
1.36 Calculation of enthalpy changes using q = mc∆T using data from experiments.
Calculate the enthalpy change of solution, ∆Hsol, of ammonium nitrate.
mass of water = 100g
specific heat capacity of water = 4.18J g −1K−1
mass of ammonium nitrate = 7.10g
initial temperature = 18.2° C
final temperature = 12.8° C
q = mc∆T
= 100 × 4.18× (12.8 − 18.2)
= −2260J
Mr(NH4NO3) = 14.0 + 4.0 + 14.0 + 48.0 = 80.0
M = 80.0g/mol
n(NH4NO3)= m/M = 7.10/80.0 = 0.089mol
0.089mol takes in 2260J
1.0mol takes in 2260/0.089 = 25 103 J
Because heat is taken in, the reaction is endothermic and ∆Hsol is positive.
∆Hsol = +25kJ/mol
It is usual to show the sign of ∆H, even when it is positive.
1.37 Propose reasons for differences between a calculated value and a literature value.
It is pure chance that the two values differ from one another. The value determined through
experimentation differs significantly from the value reported in the literature. This implies that
you should take into account any experimental mistakes that might be the cause of this
discrepancy.

5 Redox
1.1 Calculation of oxidation numbers of elements in compounds and ions.
What is the oxidation number of carbon in each of the following compounds?
CH4
Carbon is more electronegative than hydrogen. Each hydrogen has oxidation number +1, so that
of carbon is −4.
CCl4
Chlorine is more electronegative than carbon. Each chlorine has an oxidation number −1. Let the
oxidation number of carbon be x. Then x + 4(−1) = 0, so the oxidation number of carbon is +4.
What is the oxidation number of Cr and V in the following ions?
Let the unknown oxidation number be x.
Cr2O72−
2x + 7(−2) = −2, giving x = +6
VO2+
x + 2(−2) = 1, giving x = +5
1.2 The changes in oxidation numbers.

1.3 Oxidising agent and reducing agent.

Oxidising agent
Chemical reagents known as oxidizing agents, or oxidants, have the ability to oxidize other
substances. They accomplish this by either increasing the oxidation number of these substances
or removing electrons from them. Oxygen, chlorine, bromine, hydrogen peroxide, the
manganate (vii) ion in potassium manganate (vii), and the dichromate (vi) ion in potassium or
sodium dichromate (vi) are examples of common oxidizing agents.
Reducing agent
Chemical reagents known as reducing agents, or reducants, have the ability to reduce other
substances. They accomplish this by either increasing the number of electrons these substances
have or lowering their oxidation state. Metals like iron and zinc, frequently combined with acid,
sulfite ions (SO3 2-), iron(ii) ions, and iodide ions, are common reducing agents.
1.4 Identification of oxidising and reducing agents from chemical equations and changes
in oxidation number.

Dichromate(vi) ions act as oxidising agents by taking electrons from iron(ii) ions in acid
solution. An oxidising agent is itself reduced when it reacts.
Sulfite ions act as reducing agents by giving electrons to manganate(vii) ions. A reducing agent
is itself oxidised when it reacts.
1.5 Half-equations for a variety of oxidation and reduction reactions.
oxidation: Zn ⟶ Zn+ + 2e−
reduction: Fe3+ +3e− ⟶ Fe
reduction: Cu2+(aq) + 2e− → Cu(s)
oxidation: Zn(s) → Zn2+(aq) + 2e−
1.6 Construct ionic/redox equations by combining half-equations.
The two half equations are:
oxidation: Fe2+ → Fe3+ +e−
reduction: MnO4− + 5e− +8H+ → Mn2+ + 4H2O
We must multiply the first half-equation by 5 so that the electrons will cancel:
5Fe2+ → 5Fe3+ + 5e−
On addittion we than, have:
MnO4− + 5Fe2+ +8H+ → Mn2+ +5Fe3+ + 4H2O
We add the state symboles:
MnO4−(aq) + 5Fe2+ (aq) +8H+ (aq) → Mn2+ (aq) + 5Fe3+ (aq) + 4H2O(l)
1.7 The standard electrode potential.
The standard electrode (reduction) potential, of a standard half-cell is the e.m.f. of that half-cell
relative to a standard hydrogen electrode under standard conditions. Standard electrode
potentials are sometimes called standard redox potentials.
1.8 Standard conditions for pressure, temperature and concentration.
● temperature 298K (25 °C)
● gases at a pressure of 100 kPa
● solutions at a concentration of 1.0mol dm−3.
1.9 The use and features of the standard hydrogen electrode.
A standard hydrogen electrode is a half-cell in which a 1.00mol dm−3 solution of hydrogen ions
is in equilibrium with hydrogen gas at 100kPa pressure on the surface of a platinum electrode
coated with platinum black at 298K
1.10 The diagrams of the equipment used to measure standard electrode potentials, and
cell potentials, Ecell, of metals or non-metals in contact with their ions in aqueous solution,
as well as for half-cells containing ions of the same element in different oxidation states.
1.11 The strength of oxidising and reducing agents from standard electrode potential.
Oxidising agents (oxidants) take electrons and are reduced when they react.
Reducing agents (reductants) give up electrons and are oxidised when they react.
Some reagents change colour when they are oxidised which makes them useful for detecting
oxidising agents. In particular, a colourless solution of iodide ions is oxidised to iodine, which
turns the solution to a yellow-brown colour, so long as excess iodide ions are present. Iodine is
only very slightly soluble in water, but it dissolves in a solution containing iodide ions to form
the tri-iodide ion.
Some reagents change colour when they are reduced, which makes them useful for detecting
reducing agents.
1.12 Calculation of cell potentials, Ecell, from two standard electrode potential values
Calculate Ecell for a copper electrode compared with a zinc electrode.
Ecell = +0.34-(-0.76) = +1.10V
1.13 The feasibility of a reaction from Ecell values
Electrons move from the negative electrode to the positive electrode when a cell's two
electrodes are linked. Each electrode experiences chemical reactions that lower the voltage the
cell produces (the terminal potential difference), and eventually the reaction comes to an end
when the electrical potentials of the two electrodes are equal. The reaction that matches the cell
diagram occurs from left to right if Ecell is positive.
Take the cell diagram, for instance:
Zn(s)|Zn2+(aq)⢸Cu2+(aq)|Cu(s) Ecell = +1.10V
Corresponds to the reaction:
Zn(s) + Cu2+(aq) Zn2+(aq) +Cu(s)
and, as Ecell is positive, the reaction is feasible and should take place if zinc is added to copper
sulfate solution.
1.14 Changes in standard electrode potentials and subsequently, Ecell values, when non-
standard conditions are used.
A zinc half-cell is connected to a copper half-cell under standard conditions, E cell = +1.10 V and,
when the cell passes current, electrons flow from the zinc to the copper rod. If we now reduce
the concentration of the zinc ions in the zinc half-cell, the equilibrium:
Zn2+(aq) + 2e- ⇋ Zn(s)
is displaced to the left and the negative charge on the zinc rod becomes bigger. Qualitatively this
can be predicted from Le Chatelier’s Principle, and it always happens when the concentration of
the oxidised form is reduced below the standard value of 1.0moldm−3. This change in the value
of Ecell from non-standard conditions can be calculated using the Nernst equation, named after
Walther Nernst. For a half-cell against a standard hydrogen electrode at room temperature, this
equation can be written as:
 [oxidised species ]
E = E⦸ +(0.059/z)log
[reduced species ]
where z is the number of electrons added to the oxidised species to form the reduced species.
A ten-fold change in concentration only affects the E⦸ value by 0.059V for a single electron
transfer and 0.030V for the transfer of two electrons. These are very small changes and this is
the reason why E⦸ values are such a good guide to the feasibility of the reaction, even under non-
standard conditions.
1.15 The use of redox reactions in commercial storage cells with reference to the
hydrogen-oxygen fuel cell.
A fuel cell is an electrochemical cell which is continuously supplied with fuel and oxidising
agent. A fuel cell produces electric power from a fuel, directly, without having to burn it.
Fuel cells are electrochemical cells that convert a fuel's chemical energy straight into electrical
energy. Unlike other common electrochemical cells like lead-acid and lithium cells, fuel cells
have an endless supply of reactants from which to generate a constant electric current.
Hydrocarbons (like methane), alcohols, and hydrogen are among the fuels used by fuel cells. The
redox reaction between a fuel and oxygen uses energy to produce a potential difference
(voltage) inside a fuel cell. Fuel cells powered by hydrogen and alcohol have been applied to
space exploration and the development of electric vehicles.
The hydrogen-oxygen fuel cell is among the most significant fuel cells.
In theory, fuel cells are identical to the more widely used electrochemical cells. The innovation
lies in the continuous addition of new reactants (like H 2, CH3OH, and O2) to the cell, which
results in the production of H2O and occasionally CO2 or other products. The unbroken power
output and constant cell potential are made possible by this constant material flow.
All fuel cells have the great advantage of directly converting chemical energy into electricity,
with an impressive efficiency of roughly 70%. By contrast, the energy conversion efficiency of
fossil fuel-powered modern power plants and gasoline engines is only approximately 40% when
it comes to converting chemical reactions into electrical or kinetic energy.
1.16 Construction of half-equations under acidic and alkaline conditions for the reactions
in the hydrogen-oxygen fuel cell.
A hydrogen-oxygen fuel cell operating in acidic conditions is depicted in the figure below.
These types of fuel cells are used in data centers, buses, and as a backup power source for
telecommunications.
Gas containing hydrogen flows into the negative terminal, where the catalyst causes the H 2
molecules to split into individual H atoms. After that, the H atoms lose electrons to create
H+ions.
Negative terminal: H2(g) → 2H+ + 2e− Equation 1
While the hydrogen ions move through the electrolyte, the electrons enter the external circuit as
an electric current.
When oxygen reaches the positive terminal, nickel/nickel(ii) oxide catalyzes the separation of
the gas into individual oxygen atoms. Water is then created when these oxygen atoms mix with
electrons and hydrogen ions from the electrolyte.
Positive terminal: ½O2(g) + 2H+ + 2e− → H2O(l) Equation 2
The overall reaction in the hydrogen–oxygen fuel cell (obtained by adding Equations 1 and 2) is:
H2(g) + ½O2(g) → H2O(l)
Since the 1960s, NASA has used hydrogen-oxygen fuel cells to provide drinking water and
electricity on space missions. These fuel cells typically ran in an alkaline environment because
the electrolyte was aqueous potassium hydroxide.
For a hydrogen-powered alkaline fuel cell, the two reduction half-equations with electrode
potentials are as follows:
2H2O(l) + 2e− → H2(g) + 2OH−(aq) E⦸ = −0.83V
½ O2(g) + H2O(l) + 2e− → 2OH−(aq) E⦸ = +0.40V
When an alcohol such as methanol is used as the energy source in place of hydrogen in a cell
such as that shown in Figure above, the following half reactions occur at the terminals.
Negative terminal: CH3OH(l) + H2O(l) → CO2(g) + 6H+(aq) + 6e-
Positive terminal: 3/2O2(g) + 6H+(aq) + 6e- → 3H2O(l)
1.17 Measurement of the Ecell value of a redox reaction.
Calculate the Ecell of an Mg/Ag electrochemical cell using the two redox reaction equations
shown below:
Mg2+(aq) + 2e- ⇋ Mg (s) E = -2.38V
Ag+(aq) +e- ⇋ Ag(s) E = +0.80V
The Mg/Mg2+ half-cell has the more negative electrode potential, so this half-reaction will go in
the direction of oxidation. The Ag/Ag+ half-cell has the more positive electrode potential and so
will go in the direction of reduction.

1.18 Experiments to establish the end point of common redox titrations such as
Fe2+/MnO4-.
Since potassium manganate (vii) can be obtained as a pure, stable solid that reacts precisely as
shown in the following equation in an acid solution, it is frequently used to measure reducing
agents.
MnO4−(aq) + 8H+(aq) + 5e− → Mn2+(aq) + 4H2O(l)
Potassium manganate (vii) is a primary standard used to create standard solutions due to these
characteristics.
When titrating potassium manganate(vii), no indicator is needed. When a burette containing
potassium manganate(vii) solution is added, the purple MnO 4− ions quickly transform into pale
pink Mn2+ ions, which appear colorless in diluted solution. At the end, one excess MnO4− drop is
enough to permanently create a pale pink color.
I2/S2O32-
Many oxidising agents rapidly convert iodide ions to iodine by taking away electrons.
2I−(aq) → I2(aq) + 2e−
The iodine which forms can be titrated with thiosulfate ions and be reduced back to iodide ions.
I2(aq) + 2e− → 2I−(aq)
2S2O32−(aq) → S4O62−(aq) + 2e−
thiosulfate ion tetrathionate ion
These two half-equations demonstrate how one iodine molecule is reduced by two thiosulfate
ions.
With this system, any oxidizing agent that has the ability to convert iodide ions into iodine can
be quantitatively investigated. This method allows for the estimation of oxidizing agents such as
iron (iii) ions, copper (ii) ions, chlorine, and manganate (vii) ions in acid.
The process is as follows:
● Titrate the resulting iodine using a standard sodium thiosulfate solution.
● Add excess potassium iodide to a measured amount of the oxidizing agent, which
subsequently converts iodide ions to iodine.
More oxidizing agent is added to produce more iodine, which requires more thiosulfate from the
burette to react with it.
Water does not dissolve iodine. When dissolved in potassium iodide solution, it gives rise to a
dark brown concentrated solution that becomes pale yellow when diluted.
The light yellow iodine color fades at the end, leaving a colorless solution. A few drops of starch
solution added right before the endpoint sharpens the color change significantly. Iodine and
starch combine to create a deep blue color that fades towards the finish.
1.19 Calculation of quantities such as concentration from the results of the titration.
Two iron tablets (mass 1.30g) containing iron(ii) sulfate were dissolved in dilute sulfuric acid
and made up to 100cm3. 10.0cm3 of this solution required 12.00cm3 of a standard solution of
0.00500moldm-3 KMnO4 to produce a faint red colour. What is the percentage of iron in the iron
tablets? (Fe = 55.8)
1 The half-equations for the reaction are:
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O and
(Fe2+ → Fe3+ + e−) × 5
Therefore 5mol Fe2+ react with 1mol MnO4−
2 Amount of MnO4− reacting in the titration
=12.00/1000 dm3 × 0.00500 mol dm-3
Therefore the amount of Fe2+ reacting in the titration
=12.00/1000 = × 0.00500 × 5 mol
3 Amount of Fe2+ in 100cm3 of solution (2 tablets)
=12.00/1000 = × 0.00500 × 5 × 10.0 mol
=3.00/1000 = mol
4 Mass of Fe2+ in 2 tablets
=3.00/1000 mol × 55.8 g mol−1
= 0.1674g
0.1674
Therefore the percentage of iron in the tablets = ×100 =12.9%
1.30

6. Equilibria
1.1 Dynamic equilibrium in terms of the rates of forwards and backwards reactions and
the concentrations of reactants and products.
Dynamic equilibrium
Dynamic equilibrium refers to a state in which reactions between reactant and product
molecules or ions occur continuously. Products are constantly changing into reactants and
reactants are constantly changing back into products.
The forward and backward reactions continue in dynamic equilibrium, but at equal rates,
resulting in no change in the overall outcome. There is always movement at the molecular level.
It seems as though nothing is happening on a macroscopic level.
Rate of farwards and backwards reactions
The rates of the forward and backward reactions are equal at equilibrium. Reactant molecules
or ions are turning into products at the same rate that product molecules or ions are turning
into reactants.
Concentration of reactants and products
Since the rates of the forward and backward reactions are equal at equilibrium, the
concentrations stay constant. There are two ways to approach equilibrium. For example:
H2(g) + I2(g) ⟶ 2HI(g)
We can start by:
• using a mixture of colourless hydrogen gas and purple iodine vapour, or
• using only colourless hydrogen iodide gas.
When 5.00 mol of hydrogen molecules and 5.00 mol of iodine molecules react at 500 K in a
vessel of volume 1 dm3. As time passes, the purple colour of the iodine vapour fades until
equilibrium is reached. At equilibrium the mixture contains 0.68 mol of iodine, 0.68 mol of
hydrogen and 8.64 mol of hydrogen iodide.

The same equilibrium can be achieved when 10.00 mol of hydrogen iodide molecules
decompose to iodine and hydrogen iodide, So that the same equilibrium concentrations of all
three molecules are achieved.

1.2 The use of Le Chatelier’s principle to predict the qualitative effect of a change in
temperature, pressure or concentration on the position of equilibrium.
Le Chatelier’s principle
Changes in both concentration and temperature affect the position of equilibrium. When any of
the reactants or products are gases, changes in pressure may also affect the position of
equilibrium. The French chemist Henri Le Chatelier (1850–1936) observed how these factors
affect the position of equilibrium. He put forward a general rule, known as Le Chatelier’s
principle:
If one or more factors that affect an equilibrium is changed, the position of equilibrium shifts in the
direction which reduces (opposes) the change.
We can predict the effect of changing concentration and pressure by referring to the
stoichiometric equation for the reaction. We can predict the effect of changing the temperature
by referring to the enthalpy change of the reaction.
Change in concentration effect on position of equilibrium.
The system is no longer in equilibrium when the concentration of one or more reactants is
increased. The equilibrium position shifts to the right to lessen the effect of the reactant
concentration increase. More products are formed until equilibrium is restored.
When one or more product concentrations are raised, the following happens:
● The system loses equilibrium
● The equilibrium position shifts to the left to lessen the impact of the product
concentration increase
● More reactants are created until equilibrium is restored.

For example:
CH3COOH(l) + C2H5OH(l) ⟶ CH3COOC2H5(l) + H2O(l)

What occurs with increased ethanol addition?

• There is a rise in the ethanol concentration.
• Le Chatelier's principle states that in order to lower the added ethanol's concentration, some
of the ethanol must be eliminated.
• There is a rightward shift in the equilibrium position.
• More water and ethyl ethanoate are produced when ethanol and ethanoic acid react.
When we add additional water, what happens?
• There is an increase in the water content.
• Le Chatelier's principle states that in order to lower the added water's concentration, some of
the water needs to be eliminated.
• There is a shift in equilibrium to the left.
• As a result, when ethyl ethanoate and water react more, ethanol and ethanolic acid are
produced.
What transpires if we take out some water?
• There is less water in the mixture.
• Le Chatelier's principle states that in order to raise the concentration, some water must be
added.
• There is a rightward shift in the equilibrium position.
As a result, more ethanol and ethanoic acid react, producing more ethanoate and water.
Change in pressure effect on position of equilibrium
Pressure changes only have an impact on reactions in which gases are reactants or products. In
both solids and liquids, the molecules or ions are densely packed and difficult to compress. The
molecules are separated greatly in gases.
For example, consider the reaction:
2SO2(g) + O2(g) ⟶ 2SO3(g)
In the equation, there are two gas molecules on the right and three on the left.
What happens if the pressure is raised?
• Le Chatelier's principle states that the reaction must change in a way that reduces the number
of gas molecules.
• The molecules are closer together because the pressure is higher.
• There is a rightward shift in the equilibrium position.
• As a result, SO2 and O2 combine more to form SO3.
What occurs if we lower the pressure?
• Because there is less pressure, the molecules are farther apart.
• Le Chatelier's principle states that the reaction has to change in a way that produces more gas
molecules.
• There is a shift in equilibrium to the left.
• As a result, the breakdown of SO3 molecules produces more SO2 and O2 molecules.
Figure below summarises the effect of temperature changes on the position of equilibrium for
endothermic and exothermic reactions.
It should be noted that:
• A change in pressure has no effect on the position of equilibrium if there are an equal number
of gas molecules on either side of the equation.
• Only the molecules of gases matter in a reaction involving solids (or liquids) when figuring out
how pressure affects the equilibrium position.
Change in temperature effect on position of equilibrium
The decomposition of hydrogen iodide is an endothermic reaction.
2HI ⟶ H2 + I2 ∆Hr = +9.6 kJ/mol
The effect of temperature on the equilibrium concentration of hydrogen iodide and hydrogen at
equilibrium for the forward reaction is shown in figure below:

The product's concentration rises with rising temperature. The center of gravity moves to the
right. Le Chatelier's principle allows us to explain this:
• The energy of the surroundings increases with temperature
• The reaction will proceed in the direction of energy absorption, or the endothermic reaction,
in accordance with Le Chatelier's principle, which states that the reaction will go against the
increase in energy.
• There is an increase in H2 and I2 as the equilibrium moves to the right.
A drop in temperature is required to favor an exothermic reaction if an endothermic reaction is
favorably influenced by an increase in temperature:
• When the temperature drops, the surrounding energy drops as well.
Le Chatelier's principle states that a reaction will proceed in the direction that opposes an
energy decrease, or an exothermic reaction, which is a reaction in which energy is released.
Figure belo summarises the effect of temperature changes on the position of equilibrium for
endothermic and exothermic reactions.

1.3 Effect of a catalyst on the position of equilibrium

A material that quickens a chemical reaction is called a catalyst. Although catalysts shorten the
time needed to reach equilibrium, once it is reached, they have no further influence. This is as a
result of their equal increases in the forward and reverse reaction rates.
1.4 Compare and contrast the conditions used in given industrial processes.
Le Chatelier’s principle can be applied to lots of industrial processes like the production of
ethanol and methanol.
Companies need to consider the costs associated with running a reaction as well as the potential
revenue. This implies that when determining the ideal circumstances for a response, they have a
few things to consider.
Ethanol can be made via a reversible reaction between ethene and steam:
C2H4(g) + H2O(g) ⇋ C2H5OH(g) ∆H = –46 kJ/mol
The industrial conditions for the reaction are:
● a pressure of 60-70 atmospheres,
● a temperature of 300 ºC,
● a phosphoric acid catalyst.
Lower temperatures favor the forward reaction because it's an exothermic reaction. This
implies that a higher yield is obtained at lower temperatures because more ethene and steam
are converted to ethanol. However, a slower rate of reaction results from lower temperatures. If
obtaining a very high yield of ethanol is going to take ten years, then it would be foolish of you.
Therefore, the 300 ºC is a trade-off between a quicker reaction and a maximum yield.
Higher pressure, between 60 and 70 atmospheres, is preferred for the forward reaction because
it shifts the reaction to the side with fewer gas molecules. The rate of reaction also increases as
the pressure rises. Although it seems like a great idea to crank up the pressure as high as you
can, producing high pressures is expensive. To handle high pressure, you need stronger
containers and pipes. Thus, the 60–70 atmospheres represent a trade-off between yield
maximization and cost minimization.
Every time the gases go through the reactor, very little of the ethene reacts. The unreacted
ethanol is separated from the ethanol and recycled back into the reactor to save money and raw
materials.
As a result, approximately 95% of the ethene is ultimately transformed into ethanol.
Methanol is also made industrially in a reversible reaction:
2H2(g) + CO(g) ⇋ CH3OH(g) ∆H = –90 kJ/mol
Just like ethanol production, the conditions are a compromise between keeping costs low and
yield high. The conditions for this reaction are:
● a pressure of 50-100 atmospheres,
● a temperature of 250 ºC,
● a catalyst of a mixture of copper, zinc oxide and aluminium oxide.
1.5 Expressions for Kc from chemical equations.
Equilibrium expressions When hydrogen reacts with iodine in a closed tube at 500 K, the
following equilibrium is set up:
H2 + I2 ⟶ 2HI
The connection between the H2, I2, and HI equilibrium concentrations. The concentration of the
substance enclosed in square brackets in the final column is expressed mol dm −3. The following
outcomes are attained:
● A number of tubes are set up with various hydrogen and iodine starting concentrations.
● The concentrations of hydrogen, iodine, and hydrogen iodide at equilibrium are
measured after the contents of the tubes are allowed to reach equilibrium at 500 K.
The last column in Table below shows the number we get by arranging the concentrations of H 2,
I2 and HI in a particular way. We get this expression by taking the square of the concentration of
hydrogen iodide and dividing it by the concentrations of hydrogen and iodine at equilibrium. So
for the first line of data in Table below.

We call this constant the equilibrium constant, Kc. The subscript ‘c’ refers to the fact that
concentrations have been used in the calculations. There is a simple relationship which links Kc
to the equilibrium concentrations of reactants and products and the stoichiometry of the
equation. This is called an equilibrium expression.
In equilibrium expressions involving a solid, we ignore the solid. This is because its
concentration remains constant, however much solid is present.
For example:
Ag+ (aq) + Fe2+(aq) ⟶ Ag(s) + Fe3+(aq)
The equilibrium expression for this reaction is:

1.6 Calculate the value of Kc: (i) given the concentrations of the reactants and products
for a reaction at equilibrium, or (ii) given the moles of the reactants and products for a
reaction at equilibrium.
In this calculation we are given the number of moles of each of the reactants and products at
equilibrium together with the volume of the reaction mixture. Ethanol reacts with ethanoic acid
to form ethyl ethanoate and water.
CH3COOH(l) + C2H5OH(l) ⇋ CH3COOC2H5(l) + H2O(l)
500 cm3 of the reaction mixture at equilibrium contained 0.235 mol of ethanoic acid and 0.0350
mol of ethanol together with 0.182 mol of ethyl ethanoate and 0.182 mol of water. Use this data
to calculate a value of Kc for this reaction.
Step1 Write out the balanced chemical equation with the concentrations beneath each
substance.
CH3COOH(l) + C2H5OH(l) ⇋ CH3COOC2H5(l) + H2O(l)
1000 1000 1000 1000
0.235× 0.0350 × 0.182 × 0.182 ×
500 500 500 500
0.470 mol dm-3 0.070 mol dm-3 0.364 mol dm-3 0.364 mol dm-3

Step2 Write the equilibrium constant for this reaction in terms of concentrations

[CH 3COOC 2 H 5][ H 2O]

kc=
[CH 3COOH ][C 2 H 5 OH ]

Step3 Substitute the equilibrium concentrations into the expression

kc=(0.364 )׿ ¿

The units of mol dm−3 are cancelled, so Kc has no units. Therefore Kc = 4.03. Note: if there are
equal numbers of moles on the top and bottom of the equilibrium expression, you can use moles
rather than concentration in mol dm−3 in the calculation. In all other cases, if volumes are given,
the concentrations must be calculated before they are substituted into the equilibrium
expression.
1.7 Equilibrium expressions involving partial pressures
The pressure exerted by any one gas in the mixture is called its partial pressure.
Similar to how equilibrium expressions in terms of concentrations are written, equilibrium
expressions in terms of partial pressures are as well. However, there are a few differences:
• we use p for partial pressure
• the reactants and products are written as subscripts after the p
• the number of moles of particular reactants or products is written as a power after the p
• square brackets are not used
• We give the equilibrium constant the symbol Kp (the equilibrium constant in terms of partial
pressures).
For example, the equilibrium expression for the reaction:
N2(g) + 3H2(g) ⇋ 2NH3(g)

1.8 Calculation of the value of Kp given the partial pressure of the reactants and products
for a reaction at equilibrium
In this example we are given the partial pressure of each gas in the mixture. In the reaction:
2SO2(g) + O2(g) ⇋ 2SO3(g)
The equilibrium partial pressure at constant temperature are
SO2 = 1.06 × 106 Pa, O2 = 7.0 × 106 Pa, SO3 = 8.0 × 106 Pa
Calculate the value of kp for this reaction.
Step1 Write the equilibrium expression for the reaction in terms of partial pressures.

Step2 Substitute the equilibrium concentrations into the expression.

Step3 Add the correct units.

Unit = Pa × Pa / Pa× Pa ×Pa = 1/ Pa = Pa-1
Kp = 9.1× 10-6 Pa-1
1.9 Deduce the units of Kc and Kp for a given equilibrium.
Units of Kp
The units of pressure are pascals, Pa. The units of Kp depend on the form of the equilibrium
expression.
Units of kc
Each figure enclosed in a square bracket in the equilibrium expression denotes the
concentration in mol dm−3. As a result, the form of the equilibrium expression determines the Kc
units.
1.10 The effect of changes in pressure, concentration, temperature or the addition of a
catalyst on Kc and Kp values.
The effect of varying concentrations on equilibrium systems
The effect of varying one of the chemicals' concentrations in an equilibrium mixture can be
explained by the equilibrium law.
The equilibrium between chromate(vi) and dichromate(vi) ions in water is one example :

The concentration of H+(aq) is increased on the left side of the equation by adding a few drops of
concentrated acid.
For a moment, this throws the balance off. Just after adding acid, for a moment:

As more of the products are produced through the reaction of chromate(vi) ions with hydrogen
ions, the system returns to equilibrium. Very quickly, a new equilibrium is reached.
Once more:

But with the different equilibrium concentrations now having new values.
When acid is added, the "position of equilibrium shifts to the right," according to chemists
occasionally. The yellow color of the chromate(vi) ions changes to the orange color of the
dichromate(vi) ions, making the effect visible. Le Chatelier's principle foretells this. Using Kc has
the benefit of enabling quantitative predictions.
The effects of pressure changes on systems at equilibrium
Pressure changes have a noticeable impact on gaseous equilibria but are usually insignificant
for equilibria involving only solids or liquids.
A system in equilibrium responds better to a change that produces more molecules when the
pressure is lowered, and the opposite is true when the pressure is increased. Le Chatelier's
principle foretells this.
The equilibrium law can be used to quantitatively predict the effects of changing the total
pressure of a gas mixture at equilibrium. Consider the following reaction, which occurs during
the Haber process to produce ammonia:
N2 (g) + 3H2 (g) ⇋ 2NH3 (g)
The equilibrium law expression in terms of partial pressures is:

Assume that a atm, b atm, and c atm, respectively, represent the equilibrium partial pressures of
nitrogen, hydrogen, and ammonia. Adding Kp to the expression results in:

Now suppose that the total pressure is suddenly doubled. At that instant all the partial pressure
double so:

Thus, the "equilibrium constant ratio" is equal to one-quarter of Kp at that particular time.
There is no equilibrium in the system. A portion of the nitrogen and hydrogen must react to
lower their partial pressures and form more ammonia to raise its partial pressure in order to
bring the system back into balance. This continues until the numbers reach a point where the
"equilibrium constant ratio" equals Kp once more. Put differently, a rise in pressure results in a
rightward shift in the equilibrium. Thus, the direction and magnitude of the shift can be
predicted thanks to the equilibrium law.

Total 10 50 100 200

pressure/atm

% by volume of 1.2 5.6 10.6 18.3

ammonia at
equilibrium at
773k

The effects of temperature changes on systems at equilibrium

According to Le Chatelier's principle, an increase in temperature causes the equilibrium to shift
in an endothermic direction. Raising the temperature, for instance, reduces the percentage of
sulfur trioxide at equilibrium in the reaction that creates sulfur trioxide during the production
of sulfuric acid.
2SO2(g) + O2(g) ⇋ 2SO3(g) ∆H = -98 kj/mol
The equilibrium shifts to the left as the temperature rises because this is the direction in which
the reaction is endothermic. Figure below:
The effects of catalysts on systems at equilibrium
Catalysts expedite reactions without depleting themselves in the process.
It is significant to remember that a catalyst does not change the ultimate position of
equilibrium; rather, it only quickens the rate at which a reaction reaches equilibrium. Stated
differently, a catalyst offers a quicker path towards the same state of equilibrium. The dynamic
equilibrium remains unchanged when using the catalyst-assisted alternative pathway, which
has a lower activation energy but speeds up the forward and back reactions to the same degree.

7 Rate of reaction
1.1 Explain what is meant by the following terms:
i.) rate of reaction
The rate of reaction is found by measuring the rate of formation of a product or the rate of
removal of a reactant. The usual procedure for finding the rate is to measure some property of
the reaction mixture, such as its volume, and to see how this property varies with time.
The rate at which the reactions happen is not indicated by balanced chemical equations.
Chemists must conduct experiments to measure the rates of reactions under various conditions
in order to obtain this information.
Any chemical reaction results in changes to the amounts of reactants and products; reactants
vanish and products form. The rate of reaction can be calculated from the rates at which these
changes occur.
The rate of the reaction between magnesium and hydrochloric acid
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)
can be measured by:
● the rate of loss of magnesium
● the rate of loss of hydrochloric acid
● the rate of formation of magnesium chloride
● the rate of formation of hydrogen.
ii.) activation energy
The minimum energy that colliding particles must possess for a successful collision to take place
is called the activation energy of that particular reaction. The activation energy for an
exothermic reaction and an endothermic reaction can be shown on enthalpy profile diagrams
(Figure below)

1.2 Use of collision theory to explain rate of reactions with reference to changes in
concentration, pressure, temperature and surface area.
Collisions theory
The collision theory is used to explain how concentration, temperature, surface area, and
catalysts affect reaction rates. According to collision theory, particles must collide with enough
energy and in the right orientation for them to react with one another. The particles could be
molecules, ions, or atoms.
Particles of the reactant may simply bounce off one another without altering. We refer to this as
an unsuccessful collision. If there is not enough energy for the colliding particles to react, the
collision will be unsuccessful. When reactant particles collide, they might transform into
product particles if they do possess sufficient energy to undergo a reaction. This type of collision
is referred to as successful or effective.

According to the collision theory a reaction will speed up if

• the frequency of collisions increases
• the proportion of particles with energy greater than the activation energy increases.
Concentration
Reaction rates are generally inversely correlated with reactant concentrations. A higher
pressure compresses a mixture of gases and raises their concentration in gas reactions, in the
same way that a change in concentration does. Therefore, the higher the pressure in a mixture
of reacting gases, the faster the reaction.
Surface area
The surface area in contact with a liquid or gas is increased when a solid is broken up into
smaller pieces. This quickens any reaction taking place at the solid's surface. This effect holds
true for interactions between separate liquids as well.
Shaking increases the surface area for reaction by breaking up one liquid into droplets that are
then distributed throughout the other liquid.
Temperature
One of the best ways to speed up a reaction is to raise the temperature.
A temperature increase of 10°C approximately doubles the rate of reaction for several chemical
reactions occurring at room temperature (see Figure below).
Heat-plates, heating mantles, and Bunsen burners are frequently used pieces of equipment in
laboratories because they make it easy to accelerate reactions by heating the reactants. Many
industrial processes are conducted at high temperatures for the same reason.

Pressure
The effects of concentration in solutions and pressure in gas-based reactions are comparable.
There are more gas molecules in a given volume as the pressure of the reacting gases rises. This
leads to a higher number of collisions per unit of time and a quicker rate of reaction.
1.3 How a catalyst increases the rate of reaction.
A catalyst speeds up the rate of a chemical reaction without itself changing to a different
substance. The catalyst can often be recovered at the end of the reaction. A small amount of
catalyst can be effective.
It is amazing how catalysts can increase the rates of certain chemical reactions without
permanently altering them. Active catalysts in very small amounts can accelerate reactions to
produce many times their own mass of chemicals.
In order to increase the likelihood of a reaction, catalysts work by lowering or eliminating the
obstacles preventing a reaction.
Certain catalysts, like nickel metal, are capable of catalyzing a wide range of reactions.
Catalysts, however, can also be incredibly selective; they can speed up just one particular kind of
reaction. The catalysts found in living cells, called enzymes, are particularly picky.
A catalyst can interact with the reactants to form an intermediate, which is one way it can alter
the mechanism of a reaction. The intermediate is a phase in the reaction cycle where the
catalyst is released and the reactants break down to form the products. As a result, the catalyst
is free to interact with additional molecules of the reactant, and the reaction proceeds.
1.4 Term ‘initial rate’.
The initial rate or instantaneous rate at the beginning of a reaction, or when t = 0, is its initial
rate. The slope of the reactant concentration versus time curve at t = 0 is negative, which
represents the initial rate.

1.5 Maxwell-Boltzmann distribution (curve) shows in terms of molecular energies.

The Maxwell–Boltzmann distribution shows the spread of molecular kinetic energies for a gas at
a particular temperature. It shows that there is a wide spread of molecular energies and so the
molecules are moving at different speeds.
The distribution of energies for the molecules in a gas under two different sets of conditions is
depicted in the figure below. The Maxwell-Boltzmann distribution aids in the explanation of
how catalysts and temperature variations affect reaction rates.
The Maxwell–Boltzmann distribution of kinetic energies of the molecules of a gas at two
temperatures. The area under the curve gives the total number of molecules. This area does not
change as the temperature rises, so the peak height falls as the temperature rises and the curve
spreads to the right.
1.6 Significant points in a Maxwell-Boltzmann distribution e.g., the most probable energy,
the mean energy and the area under the curve.
If you plot a graph of the numbers of molecules in a gas with different kinetic energies you get a
Maxwell-Boltzmann distribution. The Maxwell-Boltzmann distribution is a theoretical model
that has been developed to explain scientific observations. It looks like this:

1.7 Maxwell-Boltzmann distributions at different temperatures.

The Maxwell–Boltzmann distribution of kinetic energies in the molecules of a gas at 300K and
310K. The area under each curve is a measure of the number of molecules. At 310K, more
molecules have enough energy to react when they collide with other molecules.
1.8 The activation energy on the distribution to show the effect of the catalyst. Use the
distribution to explain the effect of a catalyst on rate of reaction.
A catalyst functions by offering a lower activation energy alternative pathway for the reaction.
The fraction of molecules with sufficient energy to react rises when the activation energy is
lowered (Figure below).
A catalyst modifies a reaction's mechanism to increase productivity by lowering waste and
raising the yield of the desired product.

Distribution of molecular energies in a gas, showing how the proportion of molecules able to
react increases when a catalyst lowers the activation energy.
A catalyst can interact with the reactants to form an intermediate, which is one way it can alter
the mechanism of a reaction. The intermediate is a phase in the reaction cycle where the
catalyst is released and the reactants break down to form the products. As a result, the catalyst
is free to interact with additional molecules of the reactant, and the reaction proceeds (Figure
below).
Reaction profiles for a reaction a) without a catalyst and b) with a catalyst. The dip in the curve
of the pathway with a catalyst shows where an unstable intermediate forms.
1.9 Differences between homogeneous and heterogeneous catalysts.
Homogeneous catalysts
The catalyst and the reactants which can be solid, liquid, or gas are present in the same phase
during homogeneous catalysis. In order to create the final product, the catalyst first interacts
with the reactant to form an intermediate substance, which subsequently undergoes one or
more steps of decomposition or reaction with another reactant to regenerate the original
catalyst.
The chemical breakdown of ozone in the earth's upper atmosphere is an illustration of
homogeneous catalysis in action. Diatomic oxygen is produced when the relatively unstable
molecule known as ozone breaks down. The subsequent two-step mechanism fits this
decomposition reaction:
O3(g) ⟶ O2(g) + O(g)
O(g) + O3(g) ⟶ 2O2(g)
Heterogeneous catalysts
The catalyst is present in a different phase (often a solid) than the reactants in heterogeneous
catalysis. Typically, these catalysts work by providing an active surface for a reaction to take
place on. Heterogeneous catalysts catalyze reactions in both the gas and liquid phases, but they
happen on the catalyst's surface as opposed to inside the gas or liquid phase.
The following procedures are commonly involved in heterogeneous catalysis:
● Adsorption of the reactant or reactants onto the catalyst's surface
● Amplification of the reactant(s) adsorbed
● The adsorbed reactant(s)'s reaction
● Desorption of the product(s) from the catalyst's surface
1.10 A heterogeneous catalyst works in terms of providing a surface for a reaction to take
place on.
A solid catalyst is passed over by a mixture of gases in the majority of industrial processes.
Because the catalyst and reactants are in distinct phases, these catalysts are referred to as
heterogeneous catalysts. The catalyst's atoms temporarily hold the gas molecules to the solid's
surface, where they aid in the reaction. After that, the product molecules break free and are
carried away by the gas flow.
Creating catalysts that increase the efficiency of manufacturing processes and reduce waste and
energy consumption is one of the goals of the modern chemical industry. A new pathway toward
the production of a chemical product with a higher atom economy may be enabled by a novel
catalyst. It may also be possible to conduct a reaction at a lower pressure or temperature by
creating a new catalyst. Fuel is saved in this way. One of the elements that affects how profitable
large-scale chemical processes are is the cost of fuel.
1.11 Economic benefits of catalysts in industry.
A catalyst speeds up a reaction by allowing it to proceed by a different mechanism, providing a
pathway with a lower activation energy. The effect can be readily shown on the energy
distribution graph. In Figure below, if Ea is made smaller, the shaded area is much larger and so
the rate is increased.

The activation energy is lowered in the presence of a catalyst, and so many more molecules now
have enough energy to react.
Catalysts change the mechanisms of reactions, but they are not reactants and they do not appear
in the overall chemical equation. In theory, catalysts can be used over and over again, but in
practice there is some loss of catalyst. Sometimes catalysts become contaminated, sometimes
they are hard to recover completely from the products and sometimes the catalyst changes its
state, such as from lumps to a fine powder, which means that it is no longer usable.
1.12 Construction of rate equations of the form rate = k[A] x[B]y where x and y are the
orders of each reactant.
Chemists have discovered that they can create a rate equation that summarizes the findings of
their investigation into the rate of reaction. A rate equation illustrates how variations in
reactant concentrations impact a reaction's rate.
Consider the following generic reaction as an example, in which xmol A and ymol B react to
form products:
xA + yB → products
The equation that describes how the rate varies with the concentrations of the reactants takes
this form:
rate = k[A]x[B]y
where [A] and [B] represent the concentrations of the reactants in moles per cubic decimetre.
The powers m and n are the reaction orders. The reaction above is order m with respect to [A]
and order n with respect to [B]. The overall order of the reaction is (x + y).
The rate constant, k, is only constant for a particular temperature. In other words, the value of k
varies with temperature. The units of the rate constant depend on the overall order of the
reaction.
.13 The order of a reactant from:
i.) concentration versus time curves
The variation of concentration of a reactant plotted against time for a first order reaction. The
half-life for a first order reaction is a constant, so it is the same wherever it is read off the curve.
It is independent of the initial concentration.

ii.) rate versus concentration curves

The variation of reaction rate with concentration for a first order [Link] fact that the rate
of reaction is directly proportional to the concentration of the reactant means that a plot of rate
against concentration gives a straight line passing through the origin.

1.14 The overall order of a reaction from the orders of the reactants.
If the rate of a reaction is proportionate to the square of the reactant's concentration, then the
reaction is second order with respect to the reactant. This indicates that in the rate equation, the
concentration term for this reactant is raised to the power of two. The rate equation for a
second order reaction can be expressed simply as follows:
rate = k[reactant]2
This means that doubling the concentration of X increases the rate by a factor of four.
1.15 The order of a reactant from a concentration versus time curve using a half-life
method.
Plotting a concentration versus time graph and tracking how long it takes for the concentration
to drop by half is one of the simplest methods to identify a first order reaction (Figure below).
The half-life, t1/2, is this. The rate equation provides a mathematical demonstration of what
happens for a first-order reaction:
t½ = ln2/k = 0.69/k
where k is the rate constant.
This shows that, at a constant temperature, the half-life of a first order reaction is the same
wherever it is measured on a concentration–time graph. It is independent of the initial
concentration.

1.16 Calculation of: i.) the rate constant, k, from the rate equation and initial rates data.
ii.) the order of a reactant from concentrations and initial rates data.
The table below shows the results of a series of initial rate experiments for the reaction NO(g) +
CO(g) + O2(g) ⟶ NO2(g) + CO2(g).
The experiments were carried out at a constant temperature. Write down the rate equation for
the reaction and use it to calculate k at this temperature.

Experiment [NO] / mol dm–3 [CO] / mol dm–3 [O2] / mol dm–3 Initial rate / mol
number dm–3 s–1

1 2.0 × 10–2 1.0 × 10–2 1.0 × 10–2 0.17

2 6.0 × 10–2 1.0 × 10–2 1.0 × 10–2 1.53

3 2.0 × 10–2 2.0 × 10–2 1.0 × 10–2 0.17

4 4.0 × 10–2 1.0 × 10–2 2.0 × 10–2 0.68

Look at experiments 1 and 2 — when [NO] triples (and all the other concentrations stay
constant) the rate is nine times faster, and 9 = 3 2. So the reaction is second order with respect to
NO.
Look at experiments 1 and 3 — when [CO] doubles (but all the other concentrations stay
constant), the rate stays the same. So the reaction is zero order with respect to CO.
Look at experiments 1 and 4 — the rate of experiment 4 is four times faster than experiment1.
The reaction is second order with respect to [NO], so the rate will quadruple when you double
[NO]. But in experiment 4, [O2] has also been doubled. As doubling [O2] hasn’t had any additional
effect on the rate, the reaction must be zero order with respect to O2.
Now that you know the order with respect to each reactant you can write the rate equation,
Rate = k[NO]2 . You can then calculate k at this temperature by putting the concentrations and
the initial rate from one of the experiments into the rate equation.
So, using experiment 1: 0.17 = k(2.0 × 10–2)2
k = 0.17 ÷ (2.0 × 10–2)2 = 425
To work out the units of k, substitute the units of each variable into the equation for k.

And get rid of the fraction using index laws:

s-1 /mol dm-3 = mol–1 dm3 s–1
Meaning the rate constant, k = 425 mol–1 dm3 s–1.
1.17 The rate determining step in a multistep reaction from the rate equation and vice-
versa.
The rate-determining step in a multistep reaction is the slowest step: the one with the highest
activation energy.
The realization that most reactions occur in a sequence of steps rather than in a single step, as
suggested by the balanced equation, was crucial to comprehending the mechanism of a reaction.
It is surprising that a zero order reaction occurs during the breakdown of ammonia gas in the
presence of a heated platinum catalyst. How is it that the rate is unaffected by the concentration
of the single reactant? Figure below provides an illustration of one potential explanation.
Ammonia diffuses quickly to the metal's surface and is adsorbed there. This occurs quickly. On
the metal's surface, bonds break and atoms rearrange to form new molecules. The slowest
process is this one. Nitrogen and hydrogen quickly separate from the metal to enter the gas
phase after they have formed.
Thus, there is a step that determines the rate that can only occur on the platinum's surface. The
platinum's surface area, which is constant, dictates the rate of reaction. This indicates that as
long as there is sufficient ammonia to be adsorbed across the entire metal surface, the rate of
reaction will remain constant. The ammonia concentration has no bearing on the rate.
1.18 Reaction mechanism for a multistep reaction from the rate equation and chemical
equation.
The mechanism of a reaction describes how the reaction takes place, showing step by step the
bonds that break and the new bonds that form.
Hydrolysis of a primary halogenoalkane, such as 1-bromobutane, is overall second order. The
rate equation has the form: rate = k[C4H9Br][OH−].
Chemists have proposed a mechanism to explain this, which involves the C–Br bond breaking
concurrently with the nucleophile, OH−, forming a C–OH bond. In this mechanism, the single,
rate-determining step involves both reactants.

1.19 Use a graphical method and the Arrhenius equation to calculate the activation
energy when given rate constant (k) and temperature (T) data.
The decomposition of N2O5 at 308 K has a rate constant of 1.35 × 10 –4 s–1 . The Arrhenius
constant for this reaction is 4.79 × 1013 s–1 . Calculate the activation energy of this reaction. (R =
8.31 J K–1 mol–1)
First it’s a good idea to get the Arrhenius equation into a simpler form so it’s easier to use. That
means getting rid of the nasty exponential bit — so you need to take the natural log (ln) of
everything in the equation:

−Ea −Ea
K =Ae ➔ ln(k) = ln(Ae )
RT RT
−Ea
= ln(A) + ln(e )
RT
Ea
= ln(A)-
RT
Now re-arrange the equation to get Ea
Ea = (ln(A) - ln(k)) ×RT
Now you can just pop the numbers from the question into this formula:
Ea = (ln (4.79 × 1013) – ln (1.35 × 10–4)) × (8.31 × 308)
= (31.5... – (–8.91...)) × (8.31 × 308)
= 103 429.54 J mol–1
= 103 kJ mol–1 (3 s.f.)
1.20 Experiments to calculate the rate of a reaction e.g. measuring a gas volume over
time.
The reaction between hydrochloric acid and calcium carbonate may be studied using a physical
method of analysis:
CaCO3(s) 2HCl(aq) → CaCl2(aq) H2O(l) CO2(g)
A gas whose volume can be measured is released during the reaction. In Figure below, a suitable
apparatus is displayed. Plotting the volume of carbon dioxide collected against time yields a
graph whose slope, or gradient, represents the rate of reaction. The rate increases with
increasing gradient steepness. The rate is highest at the beginning of the reaction, declines, and
eventually zeroes out at the conclusion.
1.21 Use of the data from experiments to: i.) Construct plots from the experiments e.g.
volume versus time. ii.) Draw tangents on plots to obtain the gradient specified points.
Calculate the rate of reaction.
When 2g (an excess) of powdered calcium carbonate was added to 50cm3 of 0.10moldm −3
hydrochloric acid, the results shown in Table below were obtained.

Time/s 10 20 30 40 50 60 70 80
Volume of CO2
given off/cm3 25 45 60 70 75 78 80 80

The gradient of the graph at the beginning shows that 25cm 3 would be given off in 10s. This is a
rate of 2.5cm3s−1.
The rate decreases (the reaction slows down) as the reaction proceeds, because the acid
becomes more dilute. The reaction finally stops when all the acid has been used up.
1.22 Experiments using ‘clock reactions’, with the aim to calculate the order of a reactant
e.g., propanone and I2.
Iodine reacts with propanone in the presence of an acid catalyst.
I2(aq) + CH3COCH3(aq) → CH2ICOCH3(aq) + H+(aq) + I−(aq)
I first investigted the order of reaction with respect to iodine by using a titration method.
I mixed 50cm3 of 0.020mol dm-3 aqueous iodine with 50cm3 of an acidified 0.25moldm-3solution
of propanone in a flask. Every five minutes after the start, I used a pipette to remove 10.0cm 3 of
the reaction mixture which I ran into an excess of sodium hydrogencarbonate solution. Then I
titrated the iodine remaining against a standard solution of sodium thiosulfate solution. I
plotted a graph of my results, as shown in Figure below.

Why did the student remove the 10 cm3 reaction mixture samples from the flask and add them
right away to excess sodium hydrogen carbonate?
Throughout the experiment, how did the rate at which the iodine concentration changed?
What is the reaction's order in relation to iodine?
In order to confirm the first experiment's outcome and determine the order in relation to
propanone and hydrogen ions, the student conducted a second experiment consisting of
multiple runs using the initial rate method. I created a number of the acid, propanone, and
water combinations listed in Table below. Subsequently, I introduced a precisely measured
amount of iodine solution into every mixture and noted the duration required for the iodine
color to vanish. My findings are displayed in the Table below.

Run 1 Run 2 Run 3 Run 4

Volume of 2.0moldm−3
HCl(aq)/cm
20.0 10.0 20.0 20.0

Volume of 2.0moldm−3
CH3COCH3(aq)/cm3
8.0 8.0 4.0 8.0

Volume of water/cm3
0 10.0 4.0 2.0
 Volume of 0.001mol
dm−3I2(aq)/cm3
4.0 4.0 4.0 2.0

Time, t, for iodine colour

to disappear/s
115 264 243 58

Rate of reaction/cm3
iodine solution per second
0.035 0.015 0.016 0.034

Outline of the suggested mechanism to account for the rate equation for the reaction of
propanone with iodine.
1.23 Calculation of the initial rate and hence the orders.
The data on the graph below was obtained by continuously monitoring the concentration of H +
ions over the course of a reaction between a metal and an acid. Calculate the initial rate of the
reaction.

To work out the initial rate, you need to work out the gradient of the curve right at the start of
the reaction.
Draw a tangent to the curve at time = 0.
Then you just need to work out the gradient of the tangent.
gradient = change in y ÷ change in x
= (0.3 – 3.0) ÷ (0.7 – 0.0)
= –2.7 mol dm–3 ÷ 0.7 mins = –3.857... mol dm–3 min–1
So the initial rate of reaction was 3.9 mol dm–3 min–1 .
1.24 Experiments using ‘clock reactions’ at different temperatures to find the rate.
A student used the clock method for determining initial rates to find the activation for the
oxidation of iodide ions by peroxodisulfate(vi) ions:
S2O82−(aq) + 2I2- (aq) → 2SO42−(aq) + I2(aq)
In a series of experiments students kept the concentrations of the reactants constant while
varying the temperature of the reaction mixture over a range of values. The reaction mixture
included a small, measured amount of sodium thiosulfate and some starch solution, as shown in
Figure above.
Table below shows the student’s results from a series of runs with temperatures in the range
30–51°C.

Temperature/°C 30 36 39 45 51

Temperature/K 303 309

Time, t, for the 204 138 115 75 55

blue colour to
appear/s

ln(1/t) −5.32 −4.93

1000/T /K−1 3.30 3.24

8 Acids and Bases

1.1 Define the terms:
i.) Bronsted-Lowry acid
When Bronsted-Lowry acids are combined with water, they release hydrogen ions (H+), acting
as proton donors. But in water, H + ions are never found alone; instead, they are always mixed
with H2O to create hydroxonium ions, or H3O+.
ii.) Bronsted-Lowry base
Bronsted-Lowry bases act as proton acceptors. They take up hydrogen ions from water
molecules when they're in solution.
1.2 Equations to show Bronsted-Lowry conjugate acid-base pairs.
When an acid loses a proton, it transforms into its conjugate base. When a base gains a proton, it
transforms into its conjugate acid. Conjugate acid-base pairs are any two compounds consisting
of an acid and a base that can be changed via proton transfer.
NH4+(aq) + H2O(l) ⇋ NH3(aq) + H3O+(aq)
The equilibrium in a solution of the ammonium salt above involves two examples of conjugate
acid–base pairs:
● NH4 + and NH3
● H3O + and H2O
1.3 Comparision of the differences between strong and weak acids and bases.
Strong acid and strong base
In water, bases and acids separate. This merely indicates that they split into ions with opposite
charges. The strength or weakness of the acid or base determines how much dissociation
occurs. In water, strong acids almost entirely dissociate, or ionize, releasing all of the H+ ions.
Additionally, strong bases that almost entirely ionize in water include sodium hydroxide.
Example :
Hydrochloric acid is a strong acid: HCl(g) ⟶ H+ (aq) + Cl– (aq)
Sodium hydroxide is a strong base: NaOH(s) ⟶ Na+(aq) + OH–(aq)
Weak acid and weak base
Weak acids, such as citric or ethanolic, only very slightly dissociate in water, resulting in the
formation of very few H+ ions. There is a set up equilibrium that is far to the left. Ammonia and
other weak bases dissociate in water very slightly. Similar to weak acids, the equilibrium is
significantly to the left.
Example :
Ethanoic acid is a weak acid: CH3COOH(aq) ⟶ CH3COO–(aq) + H+ (aq)
Ammonia is a weak base: NH3(aq) + H2O(l) ⟶ NH4 +(aq) + OH–(aq)
1.4 pH.
The concentration of hydrogen ions in a solution is measured using the pH scale.
pH can be calculated using the following equation:
pH = – log10 [H+]
[H+] is the concentration of hydrogen ions in a solution, measured in mol dm–3
1.5 Calculations:
i.) the pH of a solution of a strong monoprotic and diprotic acids
pH of strong monoprotic acids
Calculate the pH of 0.10 mol dm–3 hydrochloric acid:
[HCl] = [H+] = 0.10 mol dm–3
So: pH = –log10 [H+]
= –log10 0.10 = 1.00
pH of strong diprotic acids
Calculate the pH of 0.25 mol dm–3 sulfuric acid:
[H+ ] = 2 × 0.25 = 0.50
So: pH = –log10 [H+]
= –log10 [0.50] = 0.30
ii.) [H+ ] for strong monoprotic and diprotic acids
Calculating[H+] from pH
[H+] = 10–pH
Monoprotic acid
hydrochloric acid have pH 1.00 calculate the [H+]
[H+] = 10–pH
= 10-1.00 mol dm–3
diprotic acid
Sulfuric acid have pH 0.30 calculate the [H+]
[H+] = 10–pH
= 10-30 mol dm–3
1.6 The ionic product of water, Kw.
Hydroxonium and hydroxide ions are produced when water separates. Thus, there is this
equilibrium in water.
O(l) + H2O(l) ⇋ H3O+(aq) + OH–(aq)
If you remove an H2O from both sides, this simplifies to:
H2O(l) ⇋ H+(aq) + OH–(aq)
And, just like for any other equilibrium reaction, you can apply the equilibrium law and write an
expression for the equilibrium constant:
Kc = ¿ ¿
Since water doesn't dissociate very much, the equilibrium is far to the left. Since there is a
greater quantity of water than H+ and OH- ions, the concentration of water is thought to remain
constant. Therefore, you can obtain a constant by multiplying the expression you wrote for K c, a
constant, by [H2O], another [Link] new constant is called the ionic product of water and
it is given the symbol Kw .
So Kw = [H+ ][OH- ]
Kw always has the same value for an aqueous solution at a given temperature.
1.7 The Kw expression for:
i.) pH of water at different temperatures
Kw always has the same value for an aqueous solution at a given temperature. For example, at
298 K (25 °C), Kw has a value of 1.00 × 10 –14 mol2 dm–6 . The value of Kw changes as the
temperature changes. In pure water, there is always one H+ ion for each OH– ion.
So [H+ ] = [OH– ].
That means if you are dealing with pure water, then you can say that:
Kw = [H+]2
ii.) pH of a basic solution
The value of Kw at 298 K is 1.0 × 10–14 mol2 dm–6. Find the pH of 0.100 mol dm–3 NaOH at 298 K.
1. Find the values of Kw and [OH–]:
The value of Kw is given in the question as 1.0 × 10–14 mol2 dm–6 NaOH is a strong base so will
donate one mole of OH– ions per mole of base.
The concentration of NaOH is 0.100 mol dm–3 so [OH-] must be 0.100 mol dm–3.
2. Substitute the values of Kw and [OH-] into the Kw equation:
Kw = [H+][OH- ]
Kw
H+ =
[OH ]
= 1.0 × 10–14 /0.100
= 1.0 × 10–13 mol dm–3
3. Substitute the value of [H+ ] into the pH equation:
pH = –log10(1.0 × 10–13)
= 13.00
iii.) Kw value at different temperatures
Kw always has the same value for an aqueous solution at a given temperature. For example, at
298 K (25 °C), Kw has a value of 1.00 × 10 –14 mol2 dm–6 . The value of Kw changes as the
temperature changes. In pure water, there is always one H+ ion for each OH– ion.
So [H+] = [OH–].
That means if you are dealing with pure water, then you can say that:
Kw = [H+]2
1.8 The reason of the change in pH of water with temperature
The number of hydrogen ions in a solution is used to calculate pH. The solution remains neutral
at a pH of 7 because the concentrations of hydrogen and hydroxyl ions are equal (1x10-7 M).
These concentrations, however, are only accurate at 25°C. The ion concentrations will change in
response to temperature changes, which will also affect the pH level. Le Chatelier's Principle
explains this response. A system that is in equilibrium will shift until it reaches equilibrium once
more if anything is changed, such as adding a reactant or changing the temperature.
The formula
H2O ⟶ H+ + OH-
The reaction is exothermic. In other words, the equation will move to the left in order to
reestablish equilibrium if the temperature of the water rises. A shift to the left raises the pH by
reducing the amount of ions in the water. Similarly, the equation would move to the right and
increase the ionic concentration and decrease pH if the temperature dropped.

The amount of ions present can change with water temperature, adjusting the pH of the solution
without making it more basic or acidic.
Water is ‘neutral’ at any pH
Temperature has no effect on the acidity of water because the ratio of hydrogen to hydroxyl
ions stays constant. Rather, the entire pH range changes, resulting in a value for neutral water
that is different from 7. At 0°C (pH of 7.47), 25°C (pH of 7.00), or 100°C (pH of 7.00), pure water
will remain neutral.

1.9 The term pka.

The logarithmic constant pka. pka is calculated from Ka in exactly the same way as pH is
calculated from [H+ ].
pka = -log10(ka)
And ka =10-pka
1.10 Calculations:
i.) the pKa of an acid.
if an acid has a Ka value of 1.50 × 10–7 mol dm–3, then
pka = -log10(ka)
pka = -log10 (1.50 × 10–7)
= 6.824
ii.) the Ka of an acid
if an acid has a pka value of 4.320, then:
ka =10-pka
ka =10-4.320
=4.79 × 10–5 mol dm–3
1.11 The Ka expression for any given weak acid
ka expression for methonic acid(HCOOH):
[ H ][ HCOO ] [ H ]❑
2❑
❑
ka = = ❑
[HCOOH ] [ HCOOH ]
1.12 Calculation of the following using the Ka expression:
i.) pH of a weak acid ii.) concentration of a weak acid iii.) Ka
Calculate the pH of 0.050 mol dm–3 methanoic acid (HCOOH). Methanoic acid has pka value 3.750
at 298 K.
Convert the pka value to a ka value
ka =10-pka
ka =10-3.750
=1.78 × 10–4 mol dm–3
ka expression for methonic acid(HCOOH):
[ H ][ HCOO ] [ H ]❑
2❑
❑
ka = = ❑
[HCOOH ] [ HCOOH ]
Rearrange it to give [H+]2 :
[H+]2 = ka [HCOOH]
=1.78 × 10–4 × 0.050
= 8.9 × 10–6
Take the square root to get [H+]:
[H+] = √ 0.0000089
=2.98 × 10–3 mol dm–3
Substitute [H+ ] into the pH equation and solve:
pH = –log (2.98 × 10–3)
= 2.526
1.13 Assumptions used in weak acid calculations
We would be tempted to believe that the initial concentration of the H3O+ ion in water is zero,
but this isn't quite accurate given how little of it there is.
It's critical to keep in mind that the H3O+ ion in this solution comes from two sources.
1.14 Interpretion of pH curves
The results of titration experiments are displayed on pH curves. They can be created by charting
the titration mixture's pH versus the amount of base added throughout the titration. A pH meter
can be used to determine the mixture's pH, and the burette's scale can be used to determine
how much base has been added.
Depending on the acid and base concentrations that were utilized, the curve's shape appears
somewhat different.
1.15 pH curves for various combinations of weak and strong acids and bases.
pH curves
The pH curves for the various mixes of strong and weak monoprotic acids and bases are
displayed in the graphs below:

With the exception of the weak acid/weak base graph, all of the graphs have a nearly vertical
portion, with the equivalence point or end point located at the middle of the section. Here, the
pH suddenly changes dramatically due to a small amount of base; all of the acid has simply been
neutralized.
The change in a weak acid/weak base titration is not as dramatic.
For this kind of titration, an indicator would change color very gradually, making it difficult to
see the precise end point. Therefore, it's usually preferable to use a pH meter to determine the
titration type's end point.
1.16 Selection of suitable indicators from a given list for a titration based on the pH
curve.
Indicators
When using an indicator, it must precisely change color when the titration is coming to an end.
Therefore, you must choose one whose color changes within a small pH range that is entirely
contained on the vertical portion of the pH curve. Thus, you would want an indicator that
changed color somewhere between pH 8 and pH 11 for the titration depicted in (Figure below):

The curve is vertical between pH 8 and pH 11 so a very small amount of alkali will cause the pH
to change from 8 to 11. So, an indicator that changes colour between pH 8 and pH 11 is needed.
Methyl orange and phenolphthalein are indicators that are often used for acid–base titrations.
1.17 Calculations of the following using pH curves and given data:
i.) the equivalence point
a pH curve with two equivalence points:

ii.) the concentration of an acid or base

25.0 cm3 of ethanedioic acid, C2H2O4 , was completely neutralised by 20.0 cm3 of 0.100 mol dm–3
KOH solution. Calculate the concentration of the ethanedioic acid solution.
1. The balanced equation for this titration reaction is:
C2H2O4 + 2KOH → K2C2O4 + 2H2O
2. You know the volume of C2H2O4 (25.0 cm3 ), the volume of KOH (20.0 cm3 ) and the
concentration of KOH (0.100 mol dm–3). You need to know the concentration of C2H2O4
3. Calculate the moles of KOH:
 concentration× volume 0.100 ×20.0
moles KOH = = = 0.002 moles
1000 1000
4. You know from the equation that you need 2 moles of KOH to neutralise 1 mole of C 2H2O4. So
0.002 moles of KOH must neutralise (0.002 ÷ 2) = 0.001 moles of C2H2O4.
5. Calculate the concentration of C2H2O4 :
mole ×1000 0.100 ×1000
Conc. C2H2O4 = = = 0.0400 mol dm–3
volume 25
1.18 Buffer solution
A buffer is a solution that resists changes in pH when small amounts of acid or alkali are added.
A buffer doesn’t stop the pH from changing completely; it does make the changes very slight
though. Buffers only work for small amounts of acid or base put too much in and they won’t be
able to cope. You get acidic buffers and basic buffers.
1.19 Explaination of the following:
i.) how a buffer solution can be made
A weak acid combined with one of its salts is one kind of buffer solution. An aqueous mixture of
sodium ethanoate and ethanolic acid is one example. Buffers between pH values 4 and 7 are
made of varying ratios of sodium ethanoate and ethanoic acid. By considering the associated
equilibria, we can comprehend the operation of a buffer solution. The acid ethanolic acid is
weak. Thus, it only results in a small concentration of ethanoate ions in solution and remains
mostly in the unionized form (CH3COOH):
CH3COOH(aq) ⇋ H+(aq) + CH3COO–(aq)
Sodium ethanoate is fully ionised in aqueous solution:
CH3COONa(s) + aq → Na+(aq) + CH3COO−(aq)
The buffer solution contains relatively high concentrations of both CH 3COOH and CH3COO–. We
say that there are reserve supplies of the acid (CH 3COOH) and its conjugate base (CH 3COO–). The
pH of a buffer solution depends on the ratio of the concentration of the acid and the
concentration of its conjugate base. If this does not change very much, the pH changes very little.
In the buffer solution ethanoic acid molecules are in equilibrium with hydrogen ions and
ethanoate ions:
CH3COOH(aq) ⇋ H+ (aq) + CH3COO–(aq)
ii.) how a buffer solution resists changes in pH
Acidic buffers have a pH of less than 7 they contain a mixture of a weak acid with one of its salts.
They can resist a change in pH when either an acid or a base is added to the solution.
Basic buffers have a pH greater than 7 and they contain a mixture of a weak base with one of its
salts. They can resist changes in pH when acid or base is added, just like acidic buffers can.
1.20 How H2CO3/HCO3- buffers blood.
Many animals depend on buffers to keep a constant pH in various parts of their bodies. In
humans, the pH of the blood is kept between 7.35 and 7.45 by a number of different buffers in
the blood:
• hydrogencarbonate ions
• haemoglobin and plasma proteins
• dihydrogenphosphate and hydrogenphosphate ions.
Our body's cells use aerobic respiration, which is the oxidation of glucose to produce energy, to
produce carbon dioxide. Blood water and carbon dioxide react to produce a solution that
contains hydrogen ions.
CO2(aq) + H2O(aq) ⇋ H+(aq) + HCO3- (aq)
The carbonic anhydrase enzyme is responsible for catalyzing this reaction. Our lungs' tiny blood
vessels quickly transform hydrogen carbonate ions into carbon dioxide and water when blood
flows through them. The lungs are where the carbon dioxide escapes.
If the generation of H+ ions is not controlled, the blood's pH will drop and "acidosis" will result.
This could impair some bodily processes and ultimately result in a coma. The most crucial blood
coagulation system is the balance between carbon dioxide and hydrogen carbonate.
1.21 Calculations:
i.) the pH of a buffer solution
A buffer solution contains 0.400 mol dm–3 methanoic acid, HCOOH, and 0.600 mol dm –3 sodium
methanoate, HCOO–Na+ . For methanoic acid, Ka = 1.6 × 10–4 mol dm–3. What is the pH of this
buffer?
Write the expression for Ka of the weak acid:
HCOOH+(aq) ⇋ H+(aq) + HCOO – (aq)
[ H ][ HCOO ]
so Ka =
[HCOOH ]
Rearrange the equation to get [H+]:
K a×[ HCOOH ]
[H+] =
[ HCOO]
0.00016 ×0.400
= = 1.07 × 10–4 mol dm–3
0.600
Use your value of [H+] to calculate the pH:
pH = – log[H+]
=– log(1.07 × 10–4)
= 3.97
ii.) the mass of salt required to give a desired pH in a buffer solution.
Find the mass of the salt which is required to give desired pH 4.25, where the pKa value is 4.20.

pH = pKa + log ( nAcid

nsalt
)
4.25 = 4.20 + log (
nAcid )
nsalt

log (
nAcid )
nsalt
= 4.25 - 4.20

log (
nAcid )
nsalt
= 0.05

( nAcid
nsalt
) = 10 = 1.1
0.05

nsalt = 0.0210 × 1.1

= 0.0231 mol
g
msalt = 0.0231 mol × 144.11
mol
msalt ≅ 3.3g
To get the desired pH (4.25), 3.3g of salt must dissolve in the solution.

9 Group 2 Metals
1.1 The reactions of group 2 metals.
Reaction with oxygen
With the exception of beryllium, the Group 2 metals burn when heated in oxygen to produce
white ionic oxides made up of M2+ and O2− ions.
Magnesium powder is used in flares and fireworks because it burns extremely brightly in the air
with an intense white flame. The white solid magnesium oxide, or MgO, is the product of the
reaction.
2Mg(s) + O2(g) → 2MgO(s)
In air, calcium also burns brilliantly, but the white solid calcium oxide, or CaO, is formed by a red
flame. The way strontium reacts is also similar.
When barium burns with too much oxygen or air, it produces a green flame and the peroxide
BaO2, which has the peroxide ion O22−.
Ba(s)+O2(s)→BaO2(s)
Reactions with water
Magnesium reacts very slowly with cold water to give the oxide and hydrogen. In steam at red
heat the reaction is rapid:
Mg(s) + H2O(g) → MgO(s) + H2(g)
The reaction does not give the hydroxide as magnesium oxide is almost insoluble in water.
Because their oxides are soluble in water, calcium, strontium and barium give the hydroxide
and hydrogen. Calcium reacts slowly, strontium more quickly and barium even more
[Link](s) + 2H2O(l) → Ba(OH)2 + H2(g)
MgO is only very slightly soluble in water. This means that when it is shaken with water, the pH
of the resulting solution is only just above 7. CaO, SrO and BaO are all more or less soluble in
water.
CaO(s) + H2O(l) → Ca2+(aq) + 2OH-(aq)
Reactions with chlorine
Beryllium reacts with chlorine on heating to form white chlorides.
Be(s) + Cl2(g) → BeCl2(s)
1.2 The reactions of group 2 oxides, hydroxides and carbonates.
All the oxides of Group 2 elements react with water to form the hydroxides.
BaO(s) + H2O(l) → Ba(OH)2(aq)
although the reaction hardly proceeds at all with magnesium because of the insolubility of the
hydroxide.
MgO(s) + H2O(l) Mg(OH)2(s)
The oxides, hydroxides and carbonates all react with dilute acids to give salts, though the
reactions between the (insoluble) carbonates and sulfuric acid become increasingly difficult due
to the insolubilities of the sulfates.
MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l)
CaCO3(s) + 2HNO3(aq) → Ca(NO3)2(aq) + H2O(l) + CO2(g)
Ba(OH)2(aq) + H2SO4(aq) → BaSO4(s) + 2H2O(l)
1.3 Trends in solubilities of group 2 hydroxides and sulfates in water.
As the proton number rises down the group, the sulfates' solubility falls:
MgSO4 > CaSO4 > SrSO4 > BaSO4. In reality, the solubilities vary between approximately
2 moldm−3 for MgSO4 and 1 × 10−5 moldm−3 for BaSO4.
The hydroxides' solubility shifts in the opposite way:
Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2 . Mg(OH)2 has a solubility of approximately
2 × 10−4 moldm−3, while Ba(OH)2 has a solubility of approximately 0.2 moldm−3.
1.4 Uses of magnesium and calcium hydroxides and barium sulfate
Uses of magnesium
In order to separate titanium from its ore, magnesium is needed. By heating carbon in a stream
of chlorine gas, the primary titanium ore, titanium(IV) oxide (TiO 2), is first transformed into
titanium(IV) chloride (TiCl4). Following fractional distillation, the titanium chloride is reduced
by magnesium in a furnace that reaches temperatures close to 1000 °C
TiCl4(g) + 2Mg(l) ⟶ Ti(s) + 2MgCl2(l).
Uses of calcium
Sulfur dioxide, a pollutant of the atmosphere, is also produced when fossil fuels are burned to
generate electricity. Wet scrubbing is the process of reacting with an alkali to extract the acidic
sulfur dioxide from waste gases.
This can be accomplished with both calcium carbonate (limestone, CaCO3) and calcium oxide
(lime, CaO). Calcium carbonate or oxide is combined with water to create a slurry. After that, the
flue gases are sprayed with it. When sulfur dioxide and alkaline slurry combine, calcium sulfite,
a solid waste product, is created.
CaO(s) + 2H2O(l) + SO2(g) ⟶ CaSO3(s) + 2H2O(l)
CaCO3(s) + 2H2O(l) + SO2(g) ⟶ CaSO3(s) + 2H2O(l) +CO2(g)
Uses of barium sulfate
To X-rays, barium sulfate is opaque; they cannot pass through it. When preparing "barium
meals," it aids in the diagnosis of oesophageal, stomach, or intestinal issues. The barium meal,
which is a suspension of barium sulfate, is swallowed by the patient. Because the tissues are
coated in barium sulfate, they appear on X-rays and reveal the organs' structures. Since barium
sulfate is insoluble and forms a suspension rather than a solution, you are unable to use other
barium compounds for this purpose because solutions containing barium ions are toxic.
1.5 Thermal decomposition.
Thermal decomposition is the name for a reaction in which a compound decomposes on
heating.
Under a Bunsen flame, compounds like metal carbonates and metal nitrates can break down.
For instance, when heated, green copper(ii) carbonate disintegrates to produce carbon dioxide
and black copper(ii) oxide. An illustration of thermal decomposition is this.
CuCO3(s) → CuO(s) + CO2(g)
1.6 Trend in the thermal decompositions of group 2 nitrates and carbonates.
The carbonates
The carbonates are all white with the general formula M 2CO3. They are unusual metal
carbonates in that they dissolve in water. Solutions of these carbonates are alkaline because the
carbonate ions remove H+ ions from water molecules to form hydrogencarbonate ions and
hydroxide ions. It is the hydroxide ions that make the solution alkaline.
CO32−(aq) + H2O(l) → HCO3−(aq) + OH−(aq)
Another unusual feature of Group 1 carbonates is that most of them do not decompose on
heating. The exception is lithium carbonate, which breaks down to the oxide and carbon dioxide
when hot.
The nitrites
The white, crystalline solids with the formula MNO3 are the nitrates of Group 1 metals. They
dissolve quite easily in water.
Compared to most other metal nitrates, the crystals of sodium and potassium nitrates are far
more resistant to breaking down when heated. These nitrates melt when heated, and when
heated further, they begin to break down and release oxygen. They only break down to the
nitrite stage.
2KNO2(s) + O2(g) → 2KNO3(s)
Nitrate of lithium is an exception. It breaks down into the oxide, nitrogen dioxide, and oxygen
like the majority of other metal nitrates.
1.7 How the trends in decomposition could be established in a laboratory
Copper(ii) sulfate crystals decompose on heating to anhydrous copper(ii) sulfate. The water
driven off condenses on the cool part of the tube.
Other metal carbonates, except those of most Group 1 metals, also decompose on heating.
Carbonates of metals below copper in the reactivity series are so unstable that they cannot exist
at room temperature. Hydrated compounds like blue copper(ii) sulfate, CuSO 4.5H2O, contain
water as part of their structure. They also decompose on heating. Fairly gentle heating causes
most hydrates to give off water vapour, which often condenses to water on the cooler parts of
the apparatus .
CuSO4.5H2O(s) → CuSO4(s) + 5H2O(g)
1.8 Equations for the thermal decomposition.

CO32−(aq) + H2O(l) → HCO3−(aq) + OH−(aq)

2KNO3(s) → 2KNO2(s) + O2(g)

10 Group 7 Elements
1.1 The physical states and colours of chlorine, bromine and iodine.
Under laboratory conditions chlorine is a yellow-green gas, bromine is a dark red liquid while
iodine is a dark grey solid.

1.2 Trend in boiling point of the group 7 elements.

As one moves down the group, the halogens' melting and boiling points rise. The information on
boiling points helps us understand how easily halogens evaporate, or how volatile they are.
Since they all have straightforward molecular structures, all of the values are rather low. Their
diatomic molecules have weak van der Waals forces between them. These forces rise with the
number of electrons in the molecules and the number of atoms in the molecules. The likelihood
of spontaneous dipoles forming within molecules and induced dipoles being produced on
nearby molecules increases with the number of electrons in a molecule. So the larger the
molecules, the stronger the van der Waals’ forces between molecules, making iodine the least
volatile and fluorine the most volatile of the halogens we are considering. The colours of the
halogens get darker going down the group.

Group VII element Melting point / °C Boiling point / °C

fluorine -220 -188

chlorine -101 -35

bromine -7 59

iodine 114 184

1.3 Trend in reactivity of the group 7 elements with reference to the halogens as
oxidising agents.
All of the halogens act as oxidizers. There is a discernible downward trend in the halogens'
reactivity as oxidizing agents based on their reactions. Iodine is the least potent oxidizing agent,
while fluorine is the most potent.
Even though the electronegativity drops down the group, halogen atoms are extremely
electronegative. They combine to form polarly bonded compounds or ionic compounds.
Ionic halides are created when s-block metals react with chlorine and bromine, giving the
halogen atoms an extra electron to occupy the outermost p subshell.
Iodine also reacts with metals to form iodides, but these iodides formed with small cations like
Li+ or highly charged cations like Al3+ are essentially covalent due to the polarisability of the
large iodide ion.
1.4 The observations of the redox reactions of group 7 elements with halide ions to show
the order of reactivity of the halogens.
Halide ions are the ions of the halogen elements in oxidation state −1. They include the fluoride
(F−), chloride (Cl−), bromide (Br−) and iodide (I−) ions.
The trend in the power of the halide ions to act as reducing agents is I− > Br− > Cl−.
Since chlorine is the most potent oxidizer among these halogens, it has the highest propensity to
produce negative ions. On the other hand, chloride ions are reluctant to return to chlorine
molecules by giving up their electrons. Hence, the least effective reducing agent is the chloride
ion.
As the least potent oxidizer, iodine has the least propensity to produce negative ions. On the
other hand, because it is most willing to give up electrons and transform back into iodine
molecules, the iodide ion is the most potent reducing agent.
1.5 Construction of chemical and ionic equations for the redox reactions of group 7
elements with halide ions.
Silver nitrate solution can be used to distinguish between halides. Silver fluoride is soluble, so
there is no precipitate on adding silver nitrate to a solution of fluoride ions. The other silver
halides are insoluble adding silver nitrate to a solution of one of these halide ions produces a
precipitate. For example:
Ag+ (aq) + Cl−(aq) → AgCl(s)
In Group 7, a more reactive halogen oxidises the ions of a less reactive halogen. So chlorine
displaces bromine from a bromide, while bromine reacts with a solution of an iodide to produce
iodine.
Br2(aq) + 2I−(aq) → 2Br−(aq) + I2(s)
1.6 Disproportionation.
The element chlorine (Cl2, oxidation number = 0) undergoes a type of redox reaction called
disproportionation when it reacts with alkali. Disproportionation can be thought of as a ‘self
reduction/ oxidation’ reaction. When chlorine reacts with dilute alkali some chlorine atoms are
reduced and some are oxidised in the same reaction. The actual reaction that takes place
depends on the temperature.
1.7 Construction of equations for the reactions of chlorine with cold and hot NaOH and
water.
Chlorine in cold alkali
Cl2(aq) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)
Cl2(aq) + H2O(l) → HCl + HClO(aq)
Chlorine in hot alkali
3Cl2(aq) + 6NaOH(aq) → 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
Cl2(aq) + H2O(l) → HCl + HClO(aq)
1.8 The use oxidation numbers to show that these reactions are disproportionation
reactions.
The chlorine undergoes disproportionation in NaOH as:
Cl2(aq) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)
The ionic equation for the reaction is:

Cl2(aq) + 2OH-(aq) → Cl-(aq) + ClO-(aq) + H2O(l)

0 -1 +1

The chlorine undergoes disproportionation in water as:

Cl2(aq) + H2O(l) → HCl + HClO(aq)
0 -1 +1

1.9 Use of chlorine in water purification.

Chlorination of water Adding a small amount of chlorine to a water supply will kill bacteria and
make the water safer to drink. The chlorine undergoes disproportionation in water:
Cl2(aq) + H2O(l) → HCl + HClO(aq)
0 -1 +1

HClO is called chloric(I) acid. It decomposes slowly in solution, producing reactive oxygen atoms
that kill bacteria in water:
HClO → HCl + O
1.10 Reactions of halide ions with concentrated sulfuric acid demonstrate the reducing
power of halide ions.
Sulfuric acid that is concentrated will react with compounds that contain Cl −, Br−, or I− ions.
These reactions need to be carried out carefully in a fume cupboard because they all produce
one or more toxic gases.
By gradually dropping concentrated sulfuric acid onto the suitable sodium salt, we can create
hydrogen chloride gas.
How much easier it is to break down the hydrogen halides as one moves down the group.
The halide in HBr and HI is being oxidized as they break down into their constituent elements.
Sulfuric acid concentrate is a reasonably potent oxidizer. While it won't oxidize HCl, it will
oxidize and break down HI and Br. Hence, any HBr or HI produced during the reaction of
concentrated sulfuric acid with sodium bromide or sodium iodide is subjected to an additional
reaction. Hydrogen bromide reduces sulfuric acid to sulfur dioxide gas when combined with
sodium bromide.
1.11 Equations for the reactions of halide ions with sulfuric acid.
NaCl(s) + H2SO4(l) → NaHSO4(s) + HCl(g)

NaBr(s) + H2SO4(l) → NaHSO4(s) + HBr(g)

NaI(s) + H2SO4(l) → NaHSO4(s) + HI(g)

1.12 Chemical tests to identify the following inorganic ions:
i.) carbonate
When dilute hydrochloric acid is added to a solution containing carbonate ions (CO 32-), the
carbonate ions in the solution will fizz. This is as a result of the acid's carbonate and hydrogen
ions reacting to produce carbon dioxide:
CO32-(aq) + 2H+ (aq) → CO2(g) + H2O(l)
Limewater can be used to test for carbon dioxide. Simply bubble carbon dioxide through a test
tube filled with limewater to see what happens. Carbon dioxide causes cloudiness in limewater.
Your solution contains carbonate ions if the limewater becomes hazy (see Figure below).

ii.) sulfate, SO42-

To identify a sulfate ion (SO42- ), you add a little dilute hydrochloric acid, followed by a barium
chloride solution, BaCl2(aq). If a white precipitate of barium sulfate forms, it means the original
compound contained a sulfate.
Ba2+ (aq) + SO42- (aq) → BaSO4(s)

iii.) ammonium, NH4+

Because ammonia gas (NH3) is alkaline, you can use a moist piece of red litmus paper to test for
it. To allow the ammonia gas to dissolve, the litmus paper needs to be wet. Paper that has
ammonia in it will become blue. Ammonia gas and water are produced when hydroxide ions are
added to a solution containing ammonium ions (NH4+) in the following way:
NH4+ (aq) + OH– (aq) →NH3(g) + H2O(l)
To determine if a material has ammonium ions (NH 4+). In a test tube containing your mystery
substance, add some diluted sodium hydroxide solution and warm the mixture slowly.
Ammonium ions must be present if ammonia is released (refer to Figure below).

iv.) halide ions, Cl− , Br− , I−

It's simple to check for halides with the silver nitrate test. Nitric acid that has been diluted is
first added to eliminate any ions that could impede the test. Next, simply add a few drops of
AgNO3(aq) silver nitrate solution. There is a precipitate (of the silver halide).
Ag+ (aq) + X– (aq) → AgX(s) ...where X is Cl, Br or I
The colour of the precipitate identifies the halide (see Figure below).

11 Period 3 Elements and Oxides

1.1 The variation in atomic radius and ionic radius.
Atomic radius variations
Throughout Period 3, the atomic radius shrinks, as seen in the figure below. There are other
eras where the same pattern is present.
With each new element over time, there is an increase of one in both the number of protons
(and thus the nuclear charge) and electrons. Every subsequent element's extra electron is added
to its atoms, and these electrons all occupy the same principal quantum shell (energy level).
This indicates that there is a roughly constant shielding effect. Therefore, the outer (valence)
shell electrons are drawn closer to the nucleus by the stronger attractive force caused by the
growing positive nuclear charge on them. As a result, the atomic radius gets smaller over time.

Ionic radius variations

the atoms of metallic elements produce positively charged ions (called cations), such as Na+ On
the other hand, the atoms of a non-metal form negatively charged ions (called anions), such as
Cl−
The third principal quantum shell, or energy level, of the positively charged ions has effectively
been lost from their original atoms. Since their atoms are larger than the cations, this is the case.
In addition, compared to their original atoms, these cations have less outer electron shielding,
which amplifies this effect. (See in figure below)

1.2 The variation in melting point and electrical conductivity of the period 3 elements
with reference to their structure and bonding
From sodium to aluminum, the electrical conductivity rises among the Period 3 metals. The
electrical conductivity then sharply decreases when one approaches silicon, referred to as a
semi-conductor, and even more sharply when one approaches the insulators sulfur and
phosphorus.
The bonding and structure of the elements must be taken into account in order to explain the
trend in melting points and electrical conductivity over time (Table below).

This can be explained by the increasing charge on the metal ions in the giant metallic lattice and
the number of electrons that each metal contributes to the "sea" of delocalized electrons. In the
lattice, each aluminum atom contributes three electrons to form Al3+ ions, whereas each
sodium atom contributes one electron to form Na+ ions. Because of the stronger electrostatic
forces between the metal's 3+ ions and the greater number of delocalized electrons holding the
giant structure together, this strengthens the metallic bonding in aluminum. Aluminum is a
better electrical conductor than sodium because it has more delocalized electrons available to
drift through the structure when the metal conducts a current.
Due to its enormous molecular structure, also known as a giant covalent structure, the element
at the center of Period 3, silicon, has the highest melting point. Strong covalent bonds hold each
silicon atom to its neighboring silicon atoms. But because there are no delocalized electrons free
to roam about within its structure, its electrical conductivity is far less than that of the metals at
the beginning of the period. Silicon is categorized as a metalloid or semi-metal.
All of the components to the right of silicon are non-metallic. They are comparatively tiny
molecules that exist. There are molecules of sulfur (S8), phosphorus (P4), and chlorine (Cl2) in
the universe. Van der Waals forces between molecules are only somewhat strong, despite the
strong covalent bonds that each molecule has with the others (see page 63). Therefore, breaking
these weak intermolecular forces and melting the elements doesn't require a lot of energy.
Phosphorus and sulfur are solids with low melting points at room temperature, while chlorine is
a gas.
1.3 Flame colours; when Na, Mg, Al, Si, S and P are burned in a flame.

Elements Reaction in air Flame color

Na Vigorous Yellow

Mg Vigorous Brilliant white

Al Slow N/A

Si Slow N/A

P Spontaneously combusts Brilliant white

S Burns steadily Blue

1.4 Construction of equations for the reactions of the period 3 elements with oxygen,
chlorine and water (water with Na and Mg only).
Reactions of Period 3 elements with oxygen
4Na(s) + O2(g) → 2Na2O(s)
2Mg(s) + O2(g) → 2MgO(s)
4Al(s) + 3O2(g) → 2Al2O3(s)
Si(s) + O2(g) → SiO2(s)
4P(s) + 5O2(g) → P4O10(s)
S(s) + O2(g) → SO2(g)
Reactions of Period 3 elements with chlorine
2Na(s) + Cl2(g) → 2NaCl(s)
Mg(s) + Cl2(g) → MgCl2(s)
2Al(s) + 3Cl2(g) → Al2Cl6(s)
Si(s) + 2Cl2(g) → SiCl4(l)
2P(s) + 5Cl2(g) → 2PCl5(l)
Reaction of sodium and magnesium with water
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
Mg(s) + 2H2O(l) → Mg(OH)2(aq) + H2(g)
Mg(s) + H2O(g) → MgO(s) + H2(g)
1.5 Observations of these reactions.
When elements from Period 3 interact with oxygen, they produce oxides. They are typically the
same group number when they are at their highest oxidation states. Thus, the oxidation state of
sodium (which belongs to Group 1) in sodium oxide is +1. In magnesium oxide, the oxidation
state of magnesium (Group 2) is +2. The exception to this is sulfur, which only has an oxidation
state of +4 when it forms SO 2. In contrast, sulfur can only have an oxidation state of +6 when it
forms SO3, which requires a high temperature and a catalyst.
The reactions between water and sodium and magnesium, two elements from Period 3. Period
3's first two elements are magnesium and sodium. Group 1 consists of sodium, and Group 2
includes magnesium.
Magnesium loses two electrons to form Mg2+ when they react, while sodium loses one electron
to form a Na+ ion. Because it requires less energy to lose one electron than it does to lose two,
sodium is more reactive than magnesium. Magnesium must therefore have additional energy,
typically heat to react.
1.6 Construction of equations for reactions of the acidic and basic period 3 oxides with
water and acid or base.
Reactions of period 3 oxides with water
Na2O(s) + H2O(l) → 2NaOH(aq)
MgO(s) + H2O(l) → Mg(OH)2(aq)
Reactions of period 3 oxides with acid or base
Acid + Base → Salt + Water
Na2O(s) + 2HCl(aq) → 2NaCl(aq) + H2O(l)
MgO(s) + H2SO4(aq) → MgSO4(aq) + H2O(l)
SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
SO3(g) + 2NaOH(aq) → Na2SO4(aq) + H2O(l)
1.7 Observations of these reactions.
Oxide ions (O2- )are present in both the ionic oxides of the metals Na and Mg.
The O2-ions take up protons from the water molecules when they dissolve in it, creating
hydroxide ions. Although both solutions are alkaline, NaOH forms a more alkaline solution than
Mg(OH)2 because it is more soluble in water.
Acidic solutions are created by the simple covalent oxides of sulfur and phosphorus, which are
non-metals. Since each acid is potent, the pH of its solutions ranges from 0 to 1 (for solutions
containing at least 1 mol dm–3). In solution, they will separate to produce a conjugate base.

1.8 The amphoteric behaviour of Al2O3

Aluminium oxide does not react or dissolve in water. However, it does react and dissolve when
added to acidic or alkaline solutions.
• With acid:
Al2O3(s) + 3H2SO4(aq) → Al2(SO4)3(aq) + 3H2O(l)
• With hot, concentrated alkali:
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)
Aluminum oxide exhibits base behavior when it reacts with an acid, forming a salt plus water,
and acid behavior when it reacts with an alkali, forming a salt. Amphoteric compounds are those
that have the ability to function as both bases and acids, such as aluminum oxide.

12 Transition Metals
1.1 The transition elements and d-block elements.
The elements from scandium to zinc inclusive comprise the 3d block. This block has 10
elements because the 3d sub-shell has five orbitals that can hold two electrons each. Zinc has
the electronic configuration [Ar]3d104s2, while scandium has [Ar]3d1 4s2. With the exception of
zinc and scandium, the remaining eight elements are referred to as transition elements because
certain of their characteristics gradually shift from those of the much less reactive metal gallium
in Group 13 to those of the reactive metal calcium in Group 2.
Transition elements are d-block elements which form one or more stable ions with incomplete d
orbitals.
Properties of the transition elements
They form some compounds containing ions with an incomplete d sub-shell.
They have variable oxidation states.
They can behave as catalysts.
They form complex ions.
They form coloured compounds.
1.2 The electronic configuration of atoms and ions of elements from Sc to Zn.

Elements
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Electronic [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar]
configurat
-ion 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2

1.3 Transition metals have varying oxidation numbers.

The oxidation states of certain transition elements, which are more commonly known. There are
numerous other oxidation states that exist and can be stabilized in certain situations.
»Chromium and manganese show their highest oxidation state in CrO 42− and MnO4−. In these,
their oxidation numbers are equal to the sum of the numbers of 3d and 4s electrons; this shows
that all of these electrons are used in the bonding.
»Manganese, iron, cobalt and copper all form M2+ ions by loss of the 4s2 electrons.
» Chromium, iron and cobalt form M3+ ions as their third ionisation energies are relatively low.
» Copper forms Cu(I) compounds as it has a single 4s electron.
1.4 Define the following terms:
i.) ligand ii.) complex ion iii.) coordination number
»A ligand is a molecule or anion bound to the central metal ion in a complex ion by co-ordinate
bonding. The transition metal ions are relatively small and have a high charge density. They
therefore attract groups containing lone pairs of electrons.
»A complex ion is an ion in which a number of molecules or anions are bound to a central metal
cation by coordinate bonds.
»The co-ordination number of a metal ion in a complex is the number of coordinate bonds to the
metal ion from the surrounding ligands.
1.5 Monodentate, bidentate and multidentate in reference to ligands.
The transition metal ions have a high charge density and are comparatively small. As a result,
groups with lone pairs of electrons are drawn to them. We refer to these groups as ligands.
Ligands are both bases and nucleophiles; the pattern of their nucleophilic strength in organic
chemistry is reflected in their ability to be attracted to metal ions. An approximate order of
attraction for common ligands is as follows:
H2O < Cl− < NH3 < CN−
Each of these four ligands uses only one lone pair of electrons to co-ordinate to a metal ion, so
they are called monodentate ligands (from the Latin, meaning ‘one-toothed’).
Some ligands can form two co-ordinate bonds from each ion or molecule to the transition metal
ion. These are called bidentate ligands.
Some ligands can form more than two co-ordinate bonds from each ion or molecule to the
transition metal ion. These are called multidentate ligands.
P-block element atoms in ligands are more electronegative than 3d-block atoms. This indicates
that the ligand draws the bond's electrons away from the metal. As a result, the charge is
dispersed outside of the ion and the metal atom becomes roughly neutral.
1.6 Formation of a complex ion.
To create a complex ion, the ligand forms a bond with the metal ion. One metal ion can combine
with six, four, or two ligands; therefore, the donation of six, four, or two pairs of electrons to the
metal ion can be thought of as the formation of a complex ion. Together with each ligand, the
metal ion forms a dative covalent bond, also known as a coordinate bond.
P-block element atoms in ligands are more electronegative than 3d-block atoms. This indicates
that the ligand draws the bond's electrons away from the metal. As a result, the charge is
dispersed outside of the ion and the metal atom becomes roughly neutral (see Figure below).

In this instance, the metal's oxidation number and the charge on the complex ion are identical.
In the event that the ligand is charged, such as a Cl − ion, the metal's oxidation number can be
determined using the same method as for any other ion. In the event that the CuCl 42− ion's
copper oxidation number is x, then:
χ + 4 ×(-1) = −2 and χ = +2
Thus, the complex ion's copper has an oxidation number of +2. It is customary to enclose the
complex ion in square brackets if a straightforward formula fails to reveal which groups are
bonded to the metal ion. One illustration of this is Cr(H 2O)6Cl3, which obscures the ligands
affixed to the chromium ion. For instance, it might be [Cr(H 2O)6]Cl3, which has three free
chloride ions but no chlorine ligands, or [Cr(H 2O)5Cl]Cl2·H2O, which has two free chloride ions
and one chlorine ligand.
1.7 The use of terms linear, square planar, tetrahedral and octahedral in reference to the
geometry of complex ions.
The co-ordination number is the total number of atoms that surround a central atom.
Consequently, the coordination number of a complex like [Cr(H 2O)6]3+ is 6. Formula ML63+ has a
complex with six pairs of electrons, and when utilizing VSEPR arguments, it takes the form of a
regular octahedron.
The ions CoCl42- and [Zn(NH3)4]2+are two examples of the tetrahedral nature of the complex.
Nonetheless, complexes containing four ligands can be square planar, indicating that
considerations beyond electron repulsion are necessary. An illustration of a square planar.
1.8 Common examples of complex ions with each shape e.g., cis-platin (square planar),
Ag+ complexes (linear).
Cisplatin is a complex of platinum(II) with two chloride ions and two ammonia molecules in a
square planar shape.

Some silver complexes have 2 co-ordinate bonds and form a linear shape.

1.9 Diagrams showing linear, square planar, tetrahedral and octahedral complex ions.

1.10 The ligands such as chloride ions might not form octahedral complexes.
An octahedral or tetrahedral shape can be formed by a complex containing a copper central
metal ion. Nevertheless, tetrahedral shapes are typically formed when larger ligands, like
chloride ions, are bonded, whereas octahedral shapes can only be formed with smaller ligands,
like ammonia and water.
1.11 i.) the charge on a complex ion from the metal ion and ligands
Keep in mind that the charges on the ions or molecules that make up the complex always add up
to the complex's total charge. Also take note of the fact that when the charge on the metal ion
grows, the coordination number of a complex frequently rises.
ii.) the charge on the metal ion from the complex ion formula
By balancing the charges of the ligands with the total charge of the complex, one can determine
the charge on the central metal ion. The coordination number and the ligands' known charges
can be used for this.
1.12 Comparision between the following types of complex ion isomers that have
monodentate or/and bidentate ligands: i.) cis-trans ii.) optical
Complexes can also show stereochemistry. A good example of this is the complex ion
[Co(en)2Br2]2+, where ‘en’ is used as an abbreviation for 1,2-diaminoethane, NH 2CH2CH2NH2. This
complex can exist in cis and trans forms. The cis form (but not the trans) has a chiral centre (the
nickel atom) and can be resolved into optical isomers (see Figure below).The overall polarity of
the trans form is zero, since all the bond dipoles cancel. The cis form does have a dipole
moment.

Ni2+ forms a complex with three 1,2-diaminoethane ligands. This has only the cis form as the
distance is too large for the ligand to stretch across the trans positions. The cis form can also be
resolved into optical isomers (see Figure below).

1.13 Cis-platin acts as an anticancer drug by reference to its interaction with DNA.
Certain types of cancer respond well to cis-platin treatment (but not trans-platin). The
[(NH3)2Cl(H2O)]+ ion is produced by the facile hydrolysis of one of the chlorine atoms in cis-
platin.
The [PtCl(guanine-DNA)(NH3)2]+ ion is produced when this ion binds to one of the four bases in
DNA, typically guanine. The displacement of chlorine from the complex by this ion allows it to
form a cross-link with another DNA chain. In cancer cells that are dividing quickly, the cross-
linking prevents DNA replication, which results in the cell's demise. Trans-platin is ineffective
for unknown reasons, though one theory is that it deactivates before it can bind to DNA.

1.14 Haemoglobin acts as a complex ion and transports oxygen around the body.
Blood contains a protein called hemoglobin, which aids in the movement of oxygen throughout
the body. Hexa-coordinated Fe2+ ions are present in it; six lone pairs are contributed to them to
create six co-ordinate bonds. Forming a circle around the Fe 2+ are nitrogen atoms, which
account for four of the lone pairs.
Haem is the name of this portion of the molecule. The molecule comprising the four nitrogen
atoms is known as a porphyrin, which is a multidentate ligand. Figure below shows how an
octahedral structure is formed when a protein known as globin binds to the Fe2+ ion along with
either an oxygen or a water molecule.

In order for the complex to carry oxygen to the required locations and then exchange it for a
water molecule, both water and oxygen in the body will attach as ligands to the Fe 2+ ions. Water
ligands take the place of oxygen molecules in the lungs, where there is a high concentration of
oxygen, to form oxyhaemoglobin, which is then transported throughout the body by the blood.
The oxygen molecules are swapped for water molecules when the oxygen-requiring hemoglobin
reaches its destination. The process then restarts when the hemoglobin reaches the lungs.
Figure below summarizes the oxygen transport process.
1.15 Origin of colour in transition metal complexes with reference to d orbitals.
The origin of colour
Since ultraviolet radiation has enough energy to excite an atom or molecule's outer electrons, all
atoms and molecules absorb light in this region of the spectrum. Because the ultraviolet region
of the spectrum is not visible, absorption there results in a colorless substance. On the other
hand, certain substances also possess outer electron levels that are close enough to one another
to provide visible light with sufficient energy to cause electronic excitation. In these conditions,
the material looks colored. White light less the color being absorbed is the color that is visible as
a result.
Therefore, the color we see is the color that compliments the color that is being absorbed.
(see figure below).
1.16 The complexes which are coloured and not coloured from electronic configurations.
An isolated transition metal atom or ion is said to have degenerate orbitals if all five of them are
at the same energy level (Figure below).
An isolated transition metal ion does not occur when ligands are present. The transition metal
ion's five d orbitals split into two sets of non-degenerate orbitals at slightly different energy
levels due to the ligands' coordinate bonding.
The electronic configuration of a Cu2+ ion is [Ar] 3d9. The distribution of the nine d electrons
among the non-degenerate orbitals formed in a complex with ligands is depicted in Figure
below. ∆E represents the energy difference between the non-degenerate d orbitals. ∆E is
included in the visible light spectrum.
Therefore, this amount of energy is absorbed by an electron in the solution containing the
Cu(H2O)62+ complex when light flows through it. It transitions into the higher of the two non-
degenerate energy levels using this energy. The remaining visible spectrum that travels through
the solution in copper complexes gives the solution a blue hue.

Numerous factors influence the precise energy difference (∆E) between the nondegenerate d
orbitals in a transition metal ion. The nature of the ligands that encircle the transition metal ion
is one of these variables.
The color of a solution containing Cu(H2O)62+ is light royal blue, as you have observed, while a
solution containing Cu(NH3)2(H2O)22+ is a very dark blue. The ammonia ligands cause the d
orbitals to split by varying amounts of energy, which results in the color change. This indicates
that there is a change in the size of ∆E, which causes electrons to jump up to higher orbitals and
absorb slightly different amounts of energy.
Consequently, a difference in colors is absorbed from visible light, so a different colour is seen.
1.17 The factors that cause complex ions to have different colours.
Charge transfer
A substance may absorb visible light to change from one bonding type to another if it contains
bonds that are slightly off the ionic and covalent boundaries.
This effect is demonstrated by certain colored solids (such as the yellow-colored AgI and the
orange-colored PbO) that contain colorless ions. Another illustration from the d block is CuO,
which is black despite the Cu2+ ion's blue color.
The deep purple color of the manganate(VII) ion, MnO 4-, is among the most prevalent instances
of color resulting from charge transfer. It is obvious that the color of manganese cannot be the
result of a d-to-d transition since the +7 oxidation state of manganese is caused by the Mn atom
losing all five of its 3d electrons as well as its two 4s electrons. Nevertheless, a charge transfer
from oxygen to manganese results from the empty d orbitals' ability to accept electrons from
the lone pairs on the oxygen ligands. The visible spectrum 500–600 nm region experiences a
broad absorption, which is correlated with the energy gap.
d-to-d transitions
Color typically appears in the d block as a result of d-to-d electronic transitions. The energy
levels of the t2g and egorbitals are near, and photons of visible light can excite electrons in the t 2g
orbitals of an octahedral complex into the egorbitals.
The electrons in the eg orbitals of tetrahedral complexes are excited into the t2g orbitals.
Applying the Planck formula,
ΔE = hf
The frequency associated with the energy difference between the orbitals corresponds to the
frequencies of visible light.
1.18 Ligand exchange reactions.
Four of the water molecules in a solution containing aqueous Cu 2+ ions are replaced by ammonia
upon the addition of ammonia, resulting in the cuprammonium ion. An illustration of a ligand-
exchange reaction is this one, in which one ligand is replaced by another:
Cu(H2O)62+(aq) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
This is a reversible reaction, and the pale blue color of the [Cu(H2O)6] 2+(aq) ] ion is restored if the
purple complex [Cu(NH3)4(H2O)2]2+(aq) ] is diluted. The NH3 and H2O molecules are vying with one
another for attachment to the copper ion. With a constant provided by the following expression,
we have equilibrium:

Since H2O is the solvent, [H2O] is in large excess and virtually a constant. We can include it in the
equilibrium constant and write:

where the stability constant is denoted by Kstab. As H2O molecules are gradually replaced by
NH3 molecules, there are stability constants for each of the equilibria, but for the purposes of
this discussion, we will only be focusing on the overall constant. The strength with which the
ligands attach to the metal atom determines the value of K stab. High electronegativity atoms
typically bind weakly, whereas low electronegativity atoms bind more strongly. Water forms
weak bonds because it binds via the highly electronegative oxygen atom, whereas the CN− ion
forms strong bonds because it binds via the carbon atom, which has much lower
electronegativity.
1.19 Comparision between the ligand exchange reactions of complex ions that contain
monodentate ligands with bidentate and multidentate ligands in terms of changes in
entropy.
The number of particles increases when bidentate or multidentate ligands are used in place of
monodentate ligands; the higher the entropy, the more particles there are. Entropy-raising
reactions have a higher probability of occurring. For this reason, compared to monodentate
ligands, multidentate ligands consistently form far more stable complexes. The chelate effect is
the term for this.
In the example above, [Ni(NH2CH2CH2NH2)3]2+ is much more stable than [Ni(NH3)6 ]2+. This isn’t
accounted for by an enthalpy change, but an increase in entropy can explain it. The number of
particles in the reaction increases from 4 to 7. This means that there is a large increase in
entropy for the reaction and therefore the [Ni(NH2CH2CH2NH2)3 ]2+ formed in the reaction is
more stable than the [Ni(NH3)6]2+ complex.

The complex formed is much more stable when the hexadentate ligand EDTA 4–replaces
monodentate or bidentate ligands. These reactions are hard to reverse because doing so would
result in a drop in the entropy of the system.
In the reaction below, the EDTA4– ligand is replacing six NH3 ligands. This increases the number
of particles in the reaction from 2 to 7.
[Cr(NH3)6]3+ + EDTA4- ⟶ [Cr(EDTA)]- + 6NH3
This means that the entropy of the system has greatly increased and so the [Cr(EDTA)] – complex
formed will be more stable than the [Cr(NH3)6]3+ complex.
1.20 The reactions of Cu2+ and Co2+ complex ions with chloride ions.
Cu(H2O)62+(aq) + 4Cl−(aq) → [CuCl4]2−(aq) + 2H2O(l)
Similar ligand exchange reactions occur with the hexaaqua cobalt(II) ion:
6H2O + [CoCl4 ]2- ⟵ [Co(H2O)6 ]2+ ⟶ [Co(NH3)6 ]2+ + 6H2O
1.21 Observations for above reactions
A more complicated ligand-exchange reaction occurs when concentrated hydrochloric acid is
added to aqueous Cu2+ ions. Here, four H2O ligands are replaced by Cl− ions, but the remaining
two water molecules are expelled, leaving the tetrahedral tetrachlorocopper(II) ion (see Figure
below):

1.22 Use of transition metals as catalysts.

A large number of transition elements or their compounds work incredibly well as catalysts.
This is explained by two characteristics of the transition elements:
» their ability to exist in more than one stable oxidation state.
» their energetically accessible vacant d orbitals which allow them to form dative bonds with
ligands.
1.23 Construction of equations showing the role of the transition metal as a catalyst in
the following reactions:
i.) SO2(g) + ½O2(g) → SO3(g) using V2O5 as the catalyst
Contact process in the manufacture of sulfuric acid:
2SO2(g) + O2(g) ⇋ 2SO3(g)
Vanadium(v) oxide, V2O5 is used as a catalyst for this reaction. The V 2O5 catalyst can reversibly
change its oxidation state
The Contact process for making sulfuric acid gets its name from the ‘contact’ between the
reacting gases and the surface of the heterogeneous catalyst. The vanadium(v) oxide catalyst is
effective because the metal can change its oxidation state reversibly. First the vanadium(v)
oxide is reduced to vanadium(iv) oxide as it oxidises sulfur dioxide to sulfur trioxide. Then the
vanadium(iv) oxide is reoxidised to vanadium(v) oxide by oxygen in the mixture of reacting
gases.
ii.) 2I- + S2O82- → I2 + 2SO42- using Fe2+ or Fe3+ ions as the catalyst
2I-(aq) + S2O82-(aq) → I2(aq) + 2SO42-(aq)
Fe2+and Fe3+ are used as a catalyst for this reaction.
In the absence of Fe3+ ions the reaction is very slow, but with Fe 3+ ions in the mixture the
reaction is many times faster. A possible mechanism is that Fe 3+ ions are reduced to Fe2+ as they
oxidise iodide ions to iodine. Then the S 2O82− ions oxidise Fe2+ ions back to Fe3+, ready to oxidise
more of the iodide ions, and so on.
12.24 Comparision between the observations for the reactions of complex ions with
dilute NaOH and dilute NH3 solutions, including in excess
Reactions with ammonia
Only the copper hydroxide precipitate will dissolve in excess ammonia, but all four metal-aqua
ions will form precipitates with ammonia. This is as a result of the ligand exchange reaction it
has with too much ammonia.

Reactions with sodium carbonate

When combined with sodium carbonate, all four metal-aqua ions will precipitate.
As CO2 is produced, bubbles will also form in the solutions containing Al 3+or Fe3+. Therefore, you
can use this test to determine whether a sample contains Fe 2+ or Fe3+ ions (which behave
identically in the other two tests). A sample containing Fe 3+ ions will release a gas, which you
will see formed as bubbles, whereas a sample containing Fe2+ ions won't.

Complex ion solutions and precipitates

 The [Fe(H2O)2]3+ complex is actually purple, but the solution appears yellow because one of the H2O ligands hydrolyses.

12.25 The ionic equations for above reactions.

[Fe(H2O)6]3+(aq) + 3NH3(aq) ⇋ Fe(OH)3(H2O)3(s) + 3NH4+(aq)
yellow solution brown precipitate
[Cu(OH)6] (aq) + 4NH3(aq) ⇋ [Cu(NH3)4(H2O)2]2+(aq) + 6OH-(aq)
4-

pale blue solution dark blue solution

Metal 2+ ions react with sodium carbonate to form insoluble metal carbonates, like this:
[M(H2O)6]2+ (aq) + CO22- (aq) ⇋ MCO3 (s) + 6H2O(l)
But, metal 3+ ions don’t form M2(CO3)3 species when you react with sodium carbonate. They are
stronger acids, so they always form hydroxide precipitates instead. The carbonate ions react
with the H3O+ ions, removing them from the solution and forming bubbles of carbon dioxide gas.
2[M(H2O)]3+ (aq) + 3CO32- (aq) ⇋ 2M(OH)3(H2O)3 (s) +3CO2 (g) + 3H2O (l)

13 Introduction to Organic Chemistry

1.1 Representation of simple organic compounds:
Structural formulas
A structural formula shows the atoms carbon by carbon, with the attached hydrogens and
functional groups.
e.g Ethane has the structural formula CH3CH3.
Displayed formulas
A displayed formula shows how all the atoms are arranged, and all the bonds between them. e.g
Displayed formula of ethane:

General formula
A general formula is an algebraic formula that can describe any member of a family of
compounds.
Molecular formulas
A molecular formula gives the actual number of atoms of each element in a molecule.
e.g Ethane has the molecular formula C2H6, each molecule is made up of 2 carbon atoms and 6
hydrogen atoms.
Empirical formulas
An empirical formula gives the simplest whole number ratio of atoms of each element in a
compound.
Skeletal formulas
A skeletal formula shows the bonds of the carbon skeleton only, with any functional groups.
Displayed and skeletal formulas of 1,5-difluoropentane:

1.2 IUPAC nomenclature to name alkanes, alkenes and halogenoalkanes

The name of the alkene beow is 2,4-dimethylhexane

Alkene

Haloalkane

1.3 Hydrocarbon.
A hydrocarbon is a compound of hydrogen and carbon only.
Crude oil, the primary raw material used in the chemical industry and the source of most fuels,
is mostly composed of hydrocarbons. Compounds with only hydrogen and carbon are known as
hydrocarbons. Alkanes and alkenes are hydrocarbons that are most prevalent and significant.
Two varieties of hydrocarbons exist.
1) Aliphatic hydrocarbons
2) Aromatic hydrocarbons
1.4 i.) aliphatic
Aliphatic hydrocarbons have branched or unbranched chains of carbon atoms or rings of carbon
atoms.
Alkanes and alkenes such as cyclohexene (Figure below) are examples of aliphatic compounds.

ii.) functional group

A functional group is the group of atoms which gives an organic compound its characteristic
properties and reactions.
One type of functional group is the hydroxyl group, or -OH group, found in ethanol. the
collection of atoms that gives an organic compound its distinctive qualities. The hydrocarbon
chain that comprises the remainder of an organic compound is comparatively non-reactive,
whereas the functional group in a molecule is in charge of most of its reactions.

iii.)saturated
Alkanes are saturated substances because their molecules only contain one bond between any
two atoms. Compounds with saturated hydrocarbon chains, such as saturated fats and fatty
acids found in food, are also referred to as "saturated." Saturated fats can cause high blood
cholesterol levels, which can clog and narrow the arteries, if consumed in excess.
Regrettably, trans fats should also be avoided as not all unsaturated fats are beneficial to health.
iv.)unsaturated
Unsaturated compounds contain one or more double or triple bonds between atoms in their
molecules.
The alkenes combine to form a class of organic compounds with a carbon–carbon double bond,
or C=C, as the functional group. Their general formula is CnH2n, and as a result, their molecules
have two fewer hydrogen atoms than the corresponding alkane. They are referred to as
unsaturated because their hydrogen content is below the maximum. In addition to alkenes,
unsaturated fats with C=C double bonds in their hydrocarbon chains are also referred to by this
term.
1.5 Homologous series.
A homologous series is a family of compounds that have the same functional group and general
formula. Consecutive members of a homologous series differ by –CH2 –.
1.6 Features of a homologous series.
A homologous series consists of molecules with the same general formula and functional group.
Certain behaviors or interactions between molecules can be predicted if you know which
homologous series a given molecule belongs to. You'll find a plethora of various homologous
series below, beginning with the most fundamental one: alkanes.
1.7 Structural isomerism
Structural isomers are compounds with the same molecular formula but different structural
formulae.
1.8 Diagrams of isomers using the various types of structural isomerism:
● Chain isomers have different chains of carbon atoms

● Position isomers have different positions of the same functional group

● Functional group isomers have different functional groups

1.9 Stereoisomerism.
Stereoisomers differ in the arrangement of their atoms in space, but they share the same
structural formula. E/Z isomerism is one kind of stereoisomerism that is present in molecules
having C=C double bonds. You must first understand a little bit more about the composition of a
C=C double bond before moving on.
1.10 Why stereoisomerism occurs for some alkenes and not others.
The atoms bound to these carbons and the carbon atoms in a C=C double bond are all planar,
meaning they lie in the same plane. They are known as trigonal planar because of their
arrangement, with the atoms linked to each double-bonded carbon forming the corners of a
hypothetical equilateral triangle:
C2H4 ethene is completely planar. The only planar unit in larger alkenes is the C=C unit.
The inability of atoms to rotate around C=C double bonds, unlike single bonds, is another
significant characteristic of these bonds. Double bonds actually don't bend all that much; they
are rather stiff. However, objects can still revolve around any one of the molecule's single bonds.

1.11 Sketch cis/trans isomers.

The following two forms of but-2-ene are therefore distinct and separate isomers:

1.12 Difference between the use of the terms cis/trans and E/Z.
Isomerism of E/Z in alkenes An example of E/Z isomerism is the restricted rotation around the
C=C double bond in alkenes. The arrangement of the groups surrounding the double bond
becomes significant if both double-bond carbons have two distinct atoms or groups attached to
them; this results in the formation of two stereoisomers. The "E-isomer" is one of these isomers,
and the "Z-isomer" is the other.
The easiest situations are those in which the same two "different groups" are attached to each
carbon in the double bond. The isomeric bond with matching groups on opposite sides of the
double bond is called the E-isomer. The Z-isomer is the one that has matching groups either on
top of the double bond or below it:
When alkenes lack two identical groups on both ends of the C-C double bond, this happens. It
occurs because one end of a C“C double bond cannot be rotated with respect to the other, in
contrast to the situation of a C—C single bond.
The following two forms of but-2-ene are therefore distinct and separate isomers:

The term "trans isomer" refers to an isomer that has both methyl groups on the opposite side of
the double bond, while the term "cis isomer" refers to an isomer that has both methyl groups on
the same side of the double bond (from the Latin word "on this side"). Cis-trans isomerism is
another term for geometrical isomerism.
1.13 Diagram of E/Z isomers by applying priority rules.
A stereoisomer of 1-bromo-1-chloro-2-fluoro-ethene

14 Alkanes
1.1 The reason of alkane’s non reactiveness
Alkane bonds are hard to break because their bond enthalpies, which are comparatively high,
are for C–C and C–H bonds. These bonds are non-polar as well. This indicates that alkanes
exhibit very little reactivity with ionic reagents in water, including reducing, oxidizing, and
alkalizing agents. Nonetheless, there are three significant alkane reactions that involve free
radicals and homolytic bond breaking. These three crucial processes are cracking, halogenation,
and combustion (burning).
1.2 Equations for the combustion reactions of alkanes.
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
C3H8(g) + 3½O2(g) → 3CO(g) + 4H2O(g)
1.3 Consequences of incomplete combustion in an internal combustion engine
Incomplete combustion occurs when a hydrocarbon burns without enough oxygen present in
the air. Instead of or in addition to carbon dioxide, this results in the production of particulate
carbon (soot) and carbon monoxide gas.
For instance, burning propane in an oxygen-poor environment releases carbon dioxide, water,
and carbon monoxide.
C3H8(g) + 3½O2(g) → 3CO(g) + 4H2O(g)
The fact that carbon monoxide gas is poisonous makes this terrible news. In red blood cells,
carbon monoxide and oxygen molecules bind to the same locations on the hemoglobin
molecules. Consequently, the body cannot transport oxygen. Fortunately, automobile catalytic
converters are able to extract carbon monoxide from exhaust gases. It is also believed that soot
can lead to respiratory issues and accumulate in engines, causing malfunctions.
1.4 Production of gasses by combustion contribute to the enhanced greenhouse effect
Carbon dioxide is produced when fossil fuels are burned. As a greenhouse gas, carbon dioxide is.
Our atmosphere's greenhouse gases are excellent at absorbing infrared energy, or heat. In order
to keep the Earth warm, they release some of the energy they absorb back into it. We refer to
this as the greenhouse effect. The majority of scientists concur that human activity is
contributing to Earth's warming by raising the atmospheric concentration of carbon dioxide. We
call this process "global warming."
1.5 Catalytic converters help reduce pollution.
The general formula for nitrogen oxides (NOx) is a group of toxic and poisonous molecules.
When nitrogen and oxygen atoms from the air react with each other in an automobile engine
due to high pressure and temperature, nitrogen monoxide is created. The following reactions'
equations illustrate how nitrogen monoxide can react to produce nitrogen dioxide.
N2(g) + O2(g) → 2NO(g)
2NO(g) + O2(g) → 2NO2(g)
1.6 i.) fractional distillation
Fractional distillation can be used to separate crude oil into more useful components, or
fractions, as it isn't very useful as is. This is the operation of fractional distillation.
At roughly 350 °C, the crude oil is first vaporized. The evaporated crude oil enters the
fractionating column at the bottom and ascends via the trays. Because of their excessively high
boiling points, the largest hydrocarbons just sink to the bottom and leave behind a sticky
residue rather than vaporizing at all. A temperature gradient is created as the crude oil vapour
cools as it ascends the fractionating column. Each fraction condenses at a distinct temperature
due to the fact that the boiling points of alkanes rise as the molecules get larger.

The fractions are drawn off at different levels in the column. The hydrocarbons with the lowest
boiling points don’t condense. They’re drawn off as gases at the top of the column.
ii.) cracking
Cracking is breaking long-chain alkanes into smaller hydrocarbons (which can include alkenes).
It involves breaking the C–C bonds.

Types of cracking
There are two types of cracking you need to know about — thermal cracking and catalytic
cracking.
Thermal cracking
It occurs at high pressure (up to 70 atm) and high temperature (up to 1000 °C). It yields a large
number of alkenes. Numerous valuable products like polymers are made from these alkenes.
One such is the ethene derivative poly(ethene).
Catalytic cracking
Zeolite catalyst, or hydrated aluminosilicate, is used in catalytic cracking at a high temperature
(approximately 500 °C) and low pressure. The principal products of this process are aromatic
hydrocarbons and the alkanes required to make motor fuels. Because the reaction can be
carried out at a lower temperature and pressure when a catalyst is used, costs are reduced.
Additionally, the catalyst quickens the rate of reaction, which saves time, which is money.
iii.) reforming
Reforming changes cyclic alkanes into arenes and straight-chain alkanes into branched-chain,
cyclic, or arenes like methylbenzene and benzene (Figure 6.2.12). One useful byproduct of the
process is hydrogen, which the refinery can use in other operations. One or more precious
metals, such as rhodium and platinum, supported on an inert substance, like aluminum oxide,
serve as the catalyst for this process. The process runs at 500 degrees Celsius.

1.7 The cracking for any given alkane.

1.8 Construction of equations showing the reforming of any given alkane.

1.9 Free radical.

In a reaction involving free radicals, the substitution of halogen atoms for hydrogen atoms in a
molecule is known as free-radical substitution.
There are three phases in free-radical chain reactions:
Initiation – the step which produces free radicals from molecules.
Propagation – steps which form products and more free radicals.
Termination – steps which remove free radicals by turning them into molecules.
1.10 Difference between homolytic and heterolytic bond fission.
The dissociation of a chemical bond into two equal fragments is known as homolytic fission. It
provides each fragment with one bond electron. During homolytic fission, energy is either
released or absorbed; this is known as the "homolytic bond dissociation energy." The
dissociation of a chemical bond into two unequal fragments is known as heterolytic fission. One
fragment receives two bond electrons, while the other fragment receives none. The main
distinction between heterolytic and homolytic fission is this. "Heterolytic bond dissociation
energy" refers to the energy that is either absorbed or released during heterolytic fission.
1.11 Equations for the initiation, propagation and termination steps of free radical
substitution of alkanes (and halogenoalkanes) with halogens.

1.12 The reason; why free radical substitution leads to a low yield of product.
There are very few radicals in the environment at any given time. The number of radicals stays
relatively constant throughout the reaction because each propagation step uses a radical and
subsequently forms a radical. Since there is little chance of two radicals colliding, very little of a
termination product, like ethane, is produced. However, the formation of any ethane at all
indicates that the suggested mechanism is accurate.

15 Alkenes
1.1 Sigma and pi bond
When two electrons in a molecule's orbital with a concentrated electron density between its
two nuclei come together, a single covalent bond called a sigma (σ) bond is formed. Around a
single bond, one can freely rotate. Two s orbitals, a s orbital and a p orbital, or two p orbitals can
overlap to form sigma bonds (Figure below).
A pi (π) bond is the kind of bond found in molecules that have double and triple bonds. The
bonding electrons are located in the π orbital, which is formed by the sideways overlap of two
atomic p orbitals. The electron density of a π bond is concentrated on both sides of the line
joining the two atoms' nuclei—one above and one below the molecule's plane—as shown in the
figure below. The rotation around a double bond is restricted by these regions of increased
electron density.

1.2 A chemical test for an alkene.

The solution quickly turns colorless when orange bromine water is shaken with an alkene (see
Figures below). Bromine is added electrophilically across the double bond to create a colorless
dibromoalkane.

Water tested for bromine. Hex-1-ene, a compound with a C=C that has reacted with the bromine
water, is contained in the test tube on the right. Hexane, a saturated material that doesn't react
with bromine water, is present in the one on the left.
1.3 Reactions of alkenes:
i.) addition of hydrogen
When an alkene, like propene, is heated to 150 °C with a nickel catalyst present, or when the
alkene is heated to room temperature with a platinum or palladium catalyst, hydrogen is added
to the C=C double bonds in the alkene.

ii.) reaction with steam

Alcohols are created when alkenes and steam interact with an acidic catalyst. For instance, the
reversible reaction between ethene and steam during the direct catalytic hydration of ethene
yields ethanol.

iii.) reaction with hydrogen halides or halogens

At room temperature, hydrogen halides react easily with alkenes to form halogenoalkanes. For
instance, bromoethane is created when hydrogen bromide and ethene react in the gas phase.
iv.) oxidation with cold KMnO4
Alkenes are oxidized by potassium manganate (vii); the results vary depending on the
circumstances. At room temperature, an alkene is changed into a diol by a potassium
manganate(vii) solution that has been diluted and acidified.

1.4 Equations for the reactions of alkenes in which [O] can be used to represent an
oxidising agent.
CH2=CH2 + H2O + [O] → HO-CH2-CH2-OH
1.5 Electrophile.
"Electro," which comes from the word "electron," and "phile," which means "loving," combine to
form the word electrophile.
An electrophile is any molecule, ion, or atom that has some kind of electron deficit. Stated
differently, an electrophile is a reagent that prefers electrons or attacks a molecule's negative.
Typically, they are neutral or positively charged species (molecules lacking an electron) with
empty orbitals. A few electrons are acceptable to electrophiles.
1.6 Draw the electrophilic addition mechanism of alkenes e.g. ethene with Br2.

1.7 Predict major and minor products of electrophilic addition between unsymmetrical
alkenes and hydrogen halides by using Markovinkov’s rule.
1.8 Explain why major and minor products are obtained in terms of the stability of
carbocations.
An analysis of the reaction's byproducts shows that 2-bromopropane is produced in much
greater amounts than 1-bromopropane when hydrogen bromide and propene react.
This suggests that the majority of the hydrogen atom from HBr is transferred to the carbon
atom of the double bond, which already has more hydrogen atoms attached to it. This pattern is
commonly known as Markovnikov's rule. Which of the two products is more likely to form can
be explained by current theories that take into account the mechanism of the reaction and the
relative stability of the intermediates (carbocations) formed.
The number of alkyl groups attached dictates the stability of the carbocation because the alkyl
groups exert an inductive effect on the carbocation.
Alkyl groups are said to have a positive inductive effect because of their slight propensity to
push electrons toward any carbon atom with which they are bonded.
1.9 Addition polymers.
Addition polymerisation is an addition reaction in which small molecules, called monomers, join
together forming a giant molecule, called a polymer.
1.10 The terms, monomer, polymer and repeat unit in relation to addition
polymerisation reactions.
A polymer is a long chain molecule made up of multiple units that repeat. Under specific
circumstances, ethylene molecules can combine to form polymer molecules. These tiny, reactive
molecules are known as monomers, and poly(ethene), which is frequently used to make carrier
bags, can be formed by the bonding of up to 10,000 ethene monomers.
The section of the polymer shown in the brackets is the repeat unit of the polymer.
This reaction is known as addition polymerization. Similar to other addition reactions, it starts
with the breaking of the π bond in each C C bond and ends with the monomers joining together.
Other alkenes also polymerise to form polymers with distinct properties. I can also think of
poly(propene) and poly(phenylethene) as additional poly(alkenes).
1.11 The repeating unit of a polymer from a monomer.

1.12 Construction of equations to show the formation of an addition polymer from a

monomer.

1.13 Monomers from a section of a polymer.

In the above figure phenylethene is a monomer of polymer polyphenylethene.

1.14 Use of polyethene and PVC.
Polyethene: use in packaging, containers and to make carrier bags.
PVC: use in guttering, water pipes, window frames, floor coverings.
1.15 Problems associated with the disposal of addition polymers.
Plastics and polymers require a lot less energy to make than equivalent products made of
materials like steel, glass, or aluminum, in addition to being incredibly useful materials for a
variety of applications. However, the question of what to do with all these materials after their
useful lives are over still needs to be answered. Reworking glass and recycling metal from old
cars, for example, are feasible but energy-intensive processes. Similarly, polymers need a safe
and suitable disposal plan that does not harm the environment. These days, there are methods
that satisfy the requirements with little to no energy expenditure.
Polyalkenes are chemically inert because they are essentially very-long-chain alkanes. Only very
slowly do they biodegrade in the environment. Certain bacteria can metabolize straight-chain
alkanes when oxidation happens somewhere along the chain, but they have more difficulty
breaking down branched-chain alkanes.
1.16 Fuels are used as solutions to the disposal problem.
There are four methods that are used, or are being developed, to allow their safe disposal.
Incineration: When a polymer burns, its enthalpy changes in a strongly exothermic manner.
Under the right conditions, incineration can yield useful energy for power generation or space
heating. The process must be carried out at a high, carefully controlled temperature in order to
avoid the formation of dangerous gases such as carbon monoxide and phosgene, or COCl2.
Because of the formation of the extremely hazardous compound "dioxin" in the absence of
meticulous conditions control, poly(chloroethene) poses a unique set of challenges. The
chlorine atoms in poly(chloroethene) must, of course, go someplace. Because hydrogen chloride
gas can be absorbed in water, it is the preferred combustion product.
Recycling: Many polymers can be melted and extracted. The recycled polymer used in this
process needs to be pure and of a single type, such as all poly(chloroethene) or all polyalkene, in
order for the materials it produces to be cheap and beneficial to the industry.
Depolymerization: Pyrolysis is the process of heating polymer chains to high temperatures in
the absence of oxygen or air, which breaks the polymer chains down into alkene units. This
process is analogous to the breakdown of long-chain hydrocarbons into alkenes. The produced
monomers can be separated and repurposed via fractional distillation.
Bacterial fermentation: Under the right conditions, a strain of bacteria can break down certain
polymers fairly quickly, most notably polyesters and polyalkenes. Usually, after being broken up
into tiny fragments, the solid polymer undergoes partial photolysis. Energy can be produced by
burning the useful combustible gases that are produced during fermentation.
`
16 Halogenoalkanes
1.1 Halogenoalkanes as primary, secondary and tertiary.
The halogen atom in a primary halogenoalkane is bound to a carbon at the end of the chain. The
halogen atom in a secondary halogenoalkane is attached to a carbon at the center of the chain
rather than at a branch.
The halogen atom in a tertiary halogenoalkane is bound to a carbon at a branch point in the
chain.
When referring to halogenoalkanes and other organic compounds, the terms primary,
secondary, and tertiary are used to indicate the locations of functional groups (Figure below).
1.2 Nucleophile.
The word nucleophile comes from combining the word nucleus with the Greek word philos,
which means "love.'' Its mean nucleophie is a nucleus loving species.
Nucleophiles are electron pair donors. An atom or molecule that contributes an electron pair to
form a covalent bond is known as a nucleophile. Another name for it is a Lewis base.
1.3 Nucleophilic substitution mechanism of halogenoalkanes with KOH, KCN and NH3.
A nucleophilic substitution mechanism using cyanide ions.

A nucleophilic substitution mechanism using ammonia

A nucleophilic substitution mechanism using hydroxide ions.

1.4 Contrastion of the different products formed when NH3 or the halogenoalkane is used
in excess.
A primary amine is created when a concentrated ammonia in ethanol solution is heated with a
halogenoalkane inside of a sealed tube. The nucleophile is the ammonia molecule. An
ammonium salt is the other product that occurs when there is an excess of ammonia.

The single electrons in the nitrogen atom of ammonia control its nucleophilicity. One problem in
this case is that a lone pair has also formed on the nitrogen atom of the primary amine, making
it even more reactive because of the inductive action of the alkyl group. As a result, there's a
chance that the halogenoalkane and the primary amine will react, creating a number of different
byproducts. Fortunately, more ammonia can be added to halt the reaction, which raises the
possibility that ammonia will interact as a nucleophile with the halogenoalkane molecules as
opposed to the amine.
1.5 Trend in reactivity of primary, secondary and tertiary halogenoalkanes.
As more carbon atoms are joined to the carbon that contains halogen, the reactivity of
halogenoalkanes rises. In other words, tertiary halogenoalkanes are the most reactive, and
primary halogenoalkanes are the least.
1.6 Trend in reactivity of chloro, bromo and iodo halogenoalkanes in terms of bond
enthalpies.
The kind of halogen present determines the reactivity of halogenoalkanes. Reactivity typically
decreases in the following order: iodine > bromine > chlorine > fluorine.
The bond gets less polar as we go from C-F to C-I. Therefore, we would anticipate that the C-F
bond would be the most reactive. But as you move from C-F to C-I, the bond enthalpy of the C-X
bond likewise drops. This indicates that as you move down the group, the reactivity rises.
1.7 Comparision between the SN1 and SN2 mechanisms.
The SN1 reaction
The hydrolysis of 2-bromo-2-methylpropane is a first-order reaction.
This indicates that doubling [RBr] doubles the rate, but doubling (or halving) [OH –] has no effect
on the rate. The rate is independent of the hydroxide concentration and solely dependent on the
bromoalkane concentration. Therefore, the rate-determining step, which is the slowest step in
the overall reaction and limits the overall rate of reaction, cannot involve hydrogen ions.
The mechanism of the reaction:

The formation of the carbocation and the bromide ion in the first step is solely dependent on the
heterolysis of the C-Br bond. Hydroxide ions are not involved in this slow step of the reaction.
The rate of the second step (carbocation + OH–) might double if [OH–] doubled. However, since
this second step moves more quickly than the first, it has no effect on the overall reaction rate.
The SN1 mechanism (Substitution, Nucleophilic, Unimolecular) refers to this series of events.
Figure below displays the SN1 reaction's reaction profile.

The SN2 reaction

The hydrolysis of bromomethane is a second-order reaction:
CH3—Br + OH− → CH3—OH + Br−
The concentration of hydroxide ions affects the rate just as much as the concentration of
bromomethane. Thus, we can infer that the rate-determining step involves both hydroxide and
bromomethane.
The process of the reaction is one that is ongoing. Unlike the carbocation in the S N1 reaction, the
complex indicated in square brackets is a transition state rather than an intermediate. At this
point in the reaction, the O—C bond is getting shorter and the C—Br bond is still getting longer.
The energy profile of the SN2 reaction is shown in Figure beow.

There is a carbocation formation stage in SN1. Then, the carbocation attracts the anion, or
negatively charged atoms or compounds. There is no intermediate formation and only a
transition stage in SN2.
1.8 Elimination reactions of symmetrical and asymmetrical halogenoalkanes with
ethanolic KOH
In ethanolic solution, the hydroxide ion acts as a base and brings about elimination of a
hydrogen halide to form an alkene instead of substitution. The mechanism shown in the
following figure.

Both of the electrons required to create a new bond with the hydrogen atom are provided by the
hydroxide ion. The two electrons from the broken C–H bond create a new bond between the two
carbon atoms. The C-Br bond breaks heterolytically at the same time. In this instance, the
bromine atom, which is released as a bromide ion, leaves the bond with both of its electrons.
The outcome of these reactions is typically a mixture of products, despite the fact that altering
the reaction conditions can favor substitution or elimination (Figure below). Furthermore,
substitution occurs more readily with primary halogenoalkanes and elimination occurs more
readily with secondary or tertiary halogenoalkanes.
1.9 Why chlorofluoroalkanes were considered harmful to the ozone layer and the
measures taken to counter this problem.
A specific category of non-reactive halogenoalkanes is well-known due to the detrimental
impact they have had on the ozone layer of Earth. Developed in the early 1900s, these
substances are known as chlorofluorocarbons (CFCs) and are purportedly safe substitutes for
harmful refrigerants like sulfur dioxide and ammonia. Using CFCs is doubly harmful because
they are potent greenhouse gases. Halogenoalkane usage is currently subject to a growing
number of restrictions due to worries about potential health risks, environmental persistence,
and ozone layer disruption.
Chlorofluorocarbons (CFCs) are compounds like CCl3F, CCl2F2, and CCl2FCClF2 that only contain
the elements chlorine, fluorine, and carbon. They don't contain any hydrogen. Certain desirable
characteristics of CFCs include their non-toxicity, non-reactivity, and lack of burning. To
accommodate various applications, CFCs with varying boiling temperatures can also be
produced. Because of these qualities, CFCs were perfect for use as the working fluid in air
conditioners and refrigerators. Additionally, they can function as blowing agents to create
bubbles in insulating foams and expanded plastics. In the past, CFCs were thought to be effective
solvents for removing grease from electrical equipment and for dry cleaning.
1.10 Construct equations showing how Cl radicals decompose ozone.
When the rate of ozone production and breakdown is equal, a steady state is established.
Because chlorine atoms function as a homogenous catalyst for ozone destruction, they upset the
equilibrium of this steady state:
Cl· + O3 → ClO· + O2
ClO· + O → Cl· + O2
By destroying the oxygen atoms required to produce more ozone through the natural formation
reaction, chlorine atoms are regenerated. Chlorine atoms thus have a twofold depleting effect on
the atmospheric concentration of ozone.
1.11 The reactivity of different halogenoalkanes using aqueous silver nitrate in ethanol.
By dissolving the halogenoalkane in ethanol and adding aqueous silver nitrate, one can study
the relative rates of hydrolysis of chloro-, bromo-, and iodoalkanes. The halide ion is liberated as
the halogenoalkane slowly hydrolyzes, forming a precipitate of silver halide:
R—X + H2O + Ag+ ⟶ R—OH + H+ + AgX(s)
Table below shows the results obtained.
Aqueous silver nitrate can be used to distinguish between organic chlorides, bromides and
iodides.

Compound Observation on reaction with Colour of precipitate

 AgNO3 + H2O in ethanol

(CH3)2CH—Cl slight cloudiness after 1 hour white

(CH3)2CH—Br cloudiness appears after a few pale cream

minutes

(CH3)2CH—I thick precipitate appears within pale yellow

a minute

17 Alcohols
1.1 Alcohols as primary, secondary and tertiary.
Alcohols can be classified as primary, secondary, or tertiary based on the carbon atom to which
the hydroxyl group (-OH) is attached. The notation 1° is applied to primary alcohols, and the -
OH group is joined to a carbon that has one alkyl group attached. The notation 2° is applied to
secondary alcohols, and the -OH group is joined to a carbon that has two alkyl groups attached.
The notation 3° is applied to tertiary alcohols, and the -OH group is joined to a carbon that has
three alkyl groups attached.

1.2 Describe the following reactions of alcohol, including conditions and products:
1.3 Construct equations for these reactions of alcohols.
i.) combustion
When ignited, the alcohols react with oxygen in the air. The products of complete combustion
are carbon dioxide and water. For example, ethanol burns with a clean blue flame in a good
supply of air:
alcohol + oxygen → carbon dioxide + water
C2H5OH + 3O2 → 2CO2 + 3H2O
ii.) substitution with PCl5, NaBr/H2SO4 or red P/I2
For chloroalkanes we can use solid phosphorus(V) chloride, PCl5 at room temperature.
C2H5OH + PCl5 → C2H5Cl + HCl + POCl3
For bromoalkanes and iodoalkanes we can make the phosphorus(III) halide, PBr 3 or PI3, in situ
using red phosphorus and bromine or iodine. These are warmed with alcohol. For example:
3C2H5OH + PI3 → 3C2H5I + H3PO3
iii.) with sodium
In the reaction with hydrogen halides, the C O bond in the alcohol breaks. However, in some
other reactions the O H bond in the alcohol breaks. The reaction with sodium metal is an
example:
C2H5OH + Na → C2H5O− Na+ + H2
iv.) dehydration using concentrated H3PO4
Alcohols can be heated with concentrated acids, like sulfuric or phosphoric, to dehydrate them
into alkenes. Since concentrated phosphoric acid produces a purer product, it is recommended.
This is because it causes fewer adverse reactions because, in contrast to concentrated sulfuric
acid, it is not also an oxidizing agent.

1.4 Different oxidation products of primary and secondary alcohols with acidified K2Cr2O7
Secondary alcohols are oxidised to ketones

Primary alcohols are oxidised to aldehydes which, in turn, are even more easily oxidised to
carboxylic acids:

1.5 Observations of the above oxidation reactions.

It is simple to oxidize primary and secondary alcohols by heating an acidified potassium
dichromate (VI) solution. Green chromium (III) ions are produced by reducing the orange
dichromate (VI) ions. However, tertiary alcohols are difficult to oxidize.
Ketones are produced by oxidizing secondary [Link] are formed when primary
alcohols are oxidized, and carboxylic acids are formed even more quickly from aldehydes.
1.6 Different conditions that influence the products formed.
Using an excess of oxidising agent, on the other hand, and heating the reaction under reflux to
prevent any escape of the aldehyde before distillation, allows the alcohol to be oxidised all the
way to the carboxylic acid.
The reaction mixture is heated to a temperature that is higher than the alcohol's boiling point
but lower than the aldehyde. As soon as the aldehyde is formed, it is allowed to distil out,
preventing additional contact with the oxidizing agent.
1.7 Chemical equations using [O] to represent the oxidising agent.
The oxidation can also be represented as a simplified equation, where [O] represents the
oxidising agent:
CH3CH2CH2OH + [O] → CH3CH2CHO + H2O
1.8 Experiments to oxidise primary and secondary alcohols.
Oxidation of a primary alcohol This takes place in two steps. In the first step, an aldehyde is
formed.

This oxidation can also be represented as a simplified equation, where [O] represents the
oxidising agent:
CH3CH2CH2OH + [O] → CH3CH2CHO + H2O
If this is the required product, the apparatus used is that shown in Figure below. This
arrangement allows the aldehyde to distil off as soon as it forms and prevents further oxidation
of the aldehyde.

The aldehyde is further oxidized to a carboxylic acid in the second stage.

In the event that a carboxylic acid is needed, a reflux condenser is employed and the primary
alcohol is heated along with the oxidizing agent (Figure below). Any volatile aldehyde is
guaranteed to condense and flow back into the flask by the reflux condenser, where an excess of
oxidizing agent guarantees total conversion into carboxylic acid.
1.9 Labelled diagrams for heating under reflux and distillation.
Apparatus for heating under reflux

Apparatus for distillation

1.10 The purpose of heating under reflux and distillation.
This process is used to oxidise a primary alcohol to a carboxylic acid. The reflux condenser
ensures that any volatile aldehyde condenses and flows back into the flask, where excess
oxidising agent ensures complete conversion.
Liquid can boil and condense in a reflux setup, returning the condensed liquid to the original
flask. The primary distinction between a reflux setup and a distillation is the condenser's
vertical location. During active reflux, the liquid stays at the solvent's (or solution's) boiling
point.
1.11 Experiments for the preparation and purification of an organic liquid
The following reaction between methanol and benzoic acid in the presence of concentrated
sulfuric acid can yield a pure sample of the ester methyl benzoate.
1. To a 50cm3 pear-shaped flask add 8g of benzoic acid, 15cm 3 of methanol and 2cm3 of
concentrated sulfuric acid. Fit the flask with a reflux condenser and boil the mixture for
about 45 minutes.
2. Cool the mixture to room temperature and pour it into a separating funnel that contains
30cm3 of cold water. Add 15cm3 of hydrocarbon solvent to the pear-shaped flask and
then pour this into the separating funnel.
3. Mix the contents of the separating funnel by vigorous shaking, releasing the pressure
carefully from time to time. Allow the contents of the flask to settle, then run the lower
aqueous layer into a conical flask.
4. Wash the hydrocarbon solvent layer in the separating funnel first with 15cm 3 of water
and secondly with 15cm3 of 0.5mol dm-3aqueous sodium carbonate.
5. Dry the hydrocarbon solvent extract over anhydrous sodium sulfate, then filter off the
solid.
6. Remove the hydrocarbon solvent by careful distillation. Collect the distillate boiling
above 190 °C and weigh your product.

1.12 Labelled diagram of a separating funnel.

1.13 The purpose of the separating funnel and the use of Na2CO3.
A separatory funnel is a piece of lab glassware used in liquid-liquid extractions to separate
(partition) the components of a mixture into two immiscible solvent phases of different
densities. It is also referred to as a separation funnel, separating funnel, or simply a "sep funnel."
Reducing the organic layer's solubility in the aqueous layer can be achieved by washing it with
sodium carbonate. This facilitates the easier separation of the organic layer.
1.14 Purpose of the drying agent.
The organic layer must be dried because it will eventually contain traces of water if separation
is used to purify a product. You can accomplish this by adding an anhydrous salt, such as
calcium chloride (CaCl2) or magnesium sulfate (MgSO4). As a drying agent, the salt binds to any
available water to become hydrated.
1.15 Boiling point as an indicator of purity.
Similar to melting temperatures for solids, boiling temperatures can be used to determine the
identity and purity of liquids; a pure liquid will distil at or within a narrow range of the expected
boiling temperature. The boiling temperature can be measured during fractional distillation as
the liquid distils over.
1.16 IUPAC nomenclature
The IUPAC nomenclature for carboxylic acids
Count the number of carbon atoms in the structure to find the name of the parent alkane. Add
the suffix "anoic acid" to the end of the parent alkane name and remove the''e'' from the end of
the alkane name.
CH3(CH2)5CO2H heptanoic acid
CH3(CH2)6CO2H octanoic acid
CH3(CH2)7CO2H nonanoic acid
The IUPAC nomenclature for esters
The name of the acid portion is given after the group name of the alkyl or aryl portion. the suffix
-ate takes the place of the parent acid's -ic ending.
CH3COOCH3 methyl ethanoate
CH3COOCH2CH3 ethyl ethanoate
The IUPAC nomenclature for acyl chlorides
When the acyl chloride moiety is predominant, acyl chlorides are identified by replacing the -ic
acid suffix in the parent carboxylic acid's name with -yl chloride.
Consequently: CH3COOH acetic acid → CH3COCl acetyl chloride. Benzoyl chloride (C6H5COCl) is
produced from benzoic acid (C6H5COOH).

18 Aromatic Chemistry
1.1 Comparision between the Kekule model with the delocalised model of the structure of
benzene.
Kekule model
Kekule proposed a model in which the bonding in the benzene ring alternated between two
equivalent structures: and We no longer need to postulate this alternation between the two
Kekulé forms since we accept that p electrons can become delocalized in many-atom p orbitals,
which are formed by the overlapping of p orbitals on adjacent atoms. It has occasionally been
suggested that the true bonding in benzene lies halfway between the two extremes symbolized
by the two Kekulé forms.
This "in-between" state is symbolized by a double-headed arrow connecting the two formulas:
The formula for benzoene is C6H6. Planar cyclic structure is a fancy term for the fact that its six
carbon atoms are bonded together into a flat ring. Every carbon atom creates a single covalent
bond with one hydrogen atom as well as the carbons next to it. Every carbon atom has a final
unpaired electron in a p-orbital that protrudes both above and below the ring's plane. A ring of
delocalized electrons is formed by the combination of the p-orbitals on each carbon atom. Since
the electrons in the ring are not associated with a particular carbon atom, they are referred to as
delocalized electrons. Since every bond in the ring is identical, they all have the same length —
140 pm. This lies in between the length of a single C–C bond (147 pm) and a double C=C bond
(135 pm).

1.2 Diagram to show the bonding in benzene with particular reference to orbital overlap.
1.3 Bond angle in benzene.
All six C—C bonds are the same length (shorter than a C—C single bond, but longer than a C“C
double bond) and the shape of the ring is a regular hexagon, with every C—C—C angle being
120°.
1.4 Explain how the Kekule model was disproven with reference to the following:
i.) reaction with Br2

ii.) bond lengths

The following physical and chemical characteristics of benzene are caused by the six-centre
delocalized pi bond:
It makes all C—C bond lengths equal, resulting in a planar, regular hexagonal shape.
It stops any of the typical addition reactions that alkenes exhibit in benzene.
iii.) hydrogenation of benzene

1.5 Comparision between the reactivity of benzene with the reactivity of alkenes.
In the air, arenes burn. Because of the high carbon to hydrogen ratio in their molecules, they
burn with a very smoky flame, in contrast to straight-chain alkanes and alkenes of similar molar
mass.
Similar to alkenes, benzoene and other arenes have a noticeable electron-dense region. This is a
single localized π bond in alkenes, and a delocalized ring of π electrons in arenes. Both arenes
and alkenes react with electrophiles in many of their reactions as a result of these similarities.
The similarities stop there, though, as arenes' overall reactions entail substitution rather than
addition, as do those of alkenes.
It is not hard to understand why arenes have trouble with addition reactions. The ring of
delocalized π electrons would be broken, for instance, if benzene and bromine reacted in an
addition reactio. The stability of the delocalized π system implies that a significantly higher
energy would be needed to break the single double bond in ethene than would be required
otherwise. Therefore, arenes mostly go through substitution processes as opposed to addition
ones in order to hold onto their delocalized π electrons.
1.6 Combustion reactions of benzene.
C6H6 + 7½ O2 → 6CO2 + 3H2O
C6H6 + 1½ O2 → 6C(s) + 3H2O
1.7 Electrophilic substitution mechanism for benzene with the following electrophiles:
i.) NO2 + (nitration)

ii.) R+ (Friedel-Crafts alkylation)

iii.) RCO+ (Friedel-Crafts acylation)

iv.) Cl+ and Br+ (halogenation)

1.8 The reagents required to form the electrophiles.

Common electrophiles reagents include positively charged ions (e.g. H+ or NO2+ ), and polar
molecules (e.g. carbonyl compounds), which have a partial positive charge.
1.9 The formation of the electrophiles.
The electrophile formation as a Br+ cation:

1.10 Convert C6H5NO2 to C6H5NH2.

1.11 Equation for this reaction using [H] to represent the reducing agent.

1.12 Comparision between the reactivity of phenol and benzene.

The −OH group in phenol activates its benzene ring and makes it more reactive than benzene
itself. A lone pair of electrons on the −OH group interacts with the delocalised electrons in the
benzene ring, releasing electrons into the ring and increasing the electron density in the ring.
This makes electrophilic attack easier so, as a result, electrophilic substitution takes place under
much milder conditions with phenol than with benzene.
1.13 Reactions between phenol and:
i.) aqueous bromine

ii.) NaOH

iii.) Na

1.14 The reactions of phenol with weak and strong bases.

Phenol has the ability to form hydrogen bonds with water due to its −OH group. Because of this,
phenol forms a soluble ionic compound when it dissolves much more readily in alkalis like
sodium hydroxide solution than it does in water. Phenol is acting like an acid in this reaction.
Phenol, however, does not react with carbonates to produce carbon dioxide or ionize
significantly in water.

At room temperature, phenol and dilute nitric acid react quickly to produce a brown mixture. 2-
and 4-nitrophenols are the reaction's principal byproducts. Take note of how much milder the
phenol nitration conditions are than the benzene nitration conditions.

1.15 The position of electrophilic substitution reactions for the following directing
groups:
i.) OH
For example, a carbonyl group like -CHO directs substitution primarily toward the meta
position, whereas a -OH group directs substitution toward the ortho and para positions.
ii.) NH2
Aniline's −NH2 group is orthogonal and paradirectional in electrophilic substitutions. Beacuse
the ortho, para attack of the electrophile forms an arenium ion, which is stabilized by the −NH 2
group.
iii.) NO2
A quick look at the resonance structures reveals that the positive charge concentrates at the
ortho-para positions because NO2 is an electron-withdrawing group. In order to facilitate
electrophilic aromatic substitution, these positions are deactivated. NO2 is a meta-director as a
result.

19 Carbonyl Compounds
1.1 Comparision between the boiling points of aldehydes and ketones with carboxylic
acids.
In carbonyl compounds, the C=O bond is polar (Figure below). Consequently, London forces and
dipole-dipole attractions are included in the intermolecular forces. Aldehydes and ketones
cannot form hydrogen bonds with one another because carbonyl compounds contain no
hydrogen atoms bound to oxygen. On the other hand, oxygen atoms in carbonyl groups and the
–OH group in water can form hydrogen bonds.
Methanal is a gas at room [Link] boils at 21 °C, so it may be a liquid or gas at
room temperature, depending on the conditions. Other common aldehydes are also liquids.
Similarly, the common ketones are liquids with boiling temperatures similar to those of the
corresponding aldehydes. The simpler aldehydes such, as methanal and ethanal, are freely
soluble in water. The simplest ketone, propanone, mixes freely with water.

Representations of the carbonyl group in aldehydes and ketones. The bond is polar because the
oxygen atom is more electronegative than carbon.
1.2 Why short-chain aldehydes, ketones and carboxylic acids are soluble in water.
The carboxylic acid group has a strong hydrogen bond with solvent molecules like water as well
as with carboxylic acid groups on other carboxylic acid molecules. Boiling points and solubilities
are two significant properties that are affected by this.
Carboxylic acids have the ability to form hydrogen-bonded dimers both in their pure liquid state
and in solution in hydrocarbon solvents that do not form hydrogen bonds.
In water, both oxygen atoms and the ¬OH hydrogen atom of carboxylic acids can hydrogen bond
with the solvent.

1.3 The nucleophilic addition mechanisms of aldehydes and ketones:

i.) with NaBH4 or LiAlH4 (using H to represent the nucleophile)

ii.) with KCN and acid

1.4 Reactions of carboxylic acids with:

i.) LiAlH4
Reducing carboxylic acids is considerably more difficult than carbonyl compounds. But the
potent reducing agent lithium tetrahydridoaluminate(iii), LiAlH4, can reduce them to primary
alcohols. Dry ether, or ethoxyethane, is used to suspend the reagent. After the reaction is
finished, any extra reducing agent is destroyed by adding diluted acid.
ii.) bases
Carboxylic acids react with carbonates (CO32–) or hydrogen carbonates (HCO3– ) to form salt,
carbon dioxide and water.

iii.) PCl5 or SOCl2

At room temperature, phosphorus pentachloride, or PCl 5, or phosphorus(v) chloride, reacts
violently with carboxylic acids. An acyl chloride is created when the –OH group is changed out
for a chlorine atom through the reaction. Hydrogen chloride gas, which fumes in damp air, is the
other product.

1.5 Reactions of carboxylic acids (using [H] to represent a reducing agent where
necessary).

1.6 Conversion of a nitrile to a carboxylic acid.

Hydrolysis of organic nitriles is done by heating in the persence of aquase sulfuric acid.
Reaction is as follow:

1.7 Comparision between the formation of esters from carboxylic acids and alcohols with
their formation from acyl chlorides and alcohols.
The formation of esters from carboxylic acids and alcohols
The formation of esters from acyl chlorides and alcohols

1.8 Formation of esters.

1.9 Comparision of the hydrolysis of esters under acidic and alkaline conditions.
An ester is hydrolyzed to produce an acid and an alcohol (or the acid's salt). The hydrolysis can
be catalyzed by bases or acids. An acid-catalyzed hydrolysis is a reversible process. This
reaction is the opposite of the one that is used to create esters from carboxylic acids.

The breakdown of an ester. When an ester, like hydrochloric acid, is heated in excess, these are
the products that result. This response can be reversed.
Because base catalysis is non-reversible, it is typically more efficient. This is because when too
much alkali reacts with the formed acid, it loses its proton. As a result, it becomes a negative ion
and is unreactive with alcohol.
The result of hydrolysing ethyl ethanoate by heating it with an aqueous alkali such as sodium
hydroxide. The salt and alcohol produced do not react with each other, so this reaction is not
reversible.
1.10 Reactions of acyl chlorides with:
i.) primary and secondary amines ii.) water iii.) phenol
Acyl chlorides have a broad range of molecular reactions. Hydrogen chloride mists are released
when an oxygen or nitrogen group replaces Cl in each of these reactions. The principal acyl
chloride reactions.

1.11 Construction of equations for reactions of acyl chlorides.

Reaction with water
Acyl chlorides react vigorously with cold water, producing a carboxylic acid.

Reaction with alcohols

Acyl chlorides react vigorously with alcohols at room temperature, producing an ester.
Reaction with ammonia
Acyl chlorides react vigorously with ammonia at room temperature, producing an amide.

1.12 The nucleophilic addition-elimination mechanisms of acyl chlorides with:

i.) primary amines

Secondary amies
ii.) water

iii.) alcohols
20 Chiral Compounds
1.1 Chiral carbon or centre.
A chiral molecule is one that cannot be superimposed on its mirror image, and a chiral carbon
atom is joined to four different groups or atoms it is alsp knwn as asymmetric carbon.

1.2 i.) chiral carbon/centre ii.) optical isomers/enantiomers

An asymmetric carbon atom is joined to four different groups or atoms. Asymmetric molecules
are molecules with no centre, axis or plane of symmetry. Asymmetric molecules are chiral and
exist in mirror-image forms. Any carbon atom with four different groups or atoms attached to it
is asymmetric and chiral. Optical isomers or enantiomers occur in pairs made up of a chiral
molecule and its non-superimposable mirror image. One mirror-image form rotates the plane of
planepolarised light clockwise. The other form rotates the plane of plane-polarised light
[Link] word ‘enantiomers’ is also used to describe mirror-image molecules that are
optical isomers. The word ‘enantiomer’ comes from a Greek word meaning ‘opposite’.
Two distinct molecules, known as enantiomers or optical isomers, can be created by arranging
the groups around chiral carbon atoms in two different ways. The enantiomers cannot be
superimposed because they are mirror images and cannot be turned in any direction. Molecules
are achiral and do not exhibit optical isomerism if they can be superimposed.

1.3 Chiral carbons/centers in organic compounds.

1.4 Diagram of enantiomers using the 3D dashed and wedges style bonds.

1.5 Method of using plane-polarised light to distinguish between two enantiomers.

A light beam becomes polarised after passing through a sheet of Polaroid, the material used to
make some sunglasses. The Polaroid prevents vibrations of the light waves in all but one plane.
So, in polarised light, all the waves are vibrating in the same plane (Figure below).

After traveling through a Polaroid sheet, light is said to be plane polarized. If the second
Polaroid sheet is aligned in the same manner as the first, all of the polarized beam passes
through when the polarized light is directed towards it. Nevertheless, if the second sheet is
turned 90 degrees with respect to the first sheet, no light can pass through (Figure below).

The rotation of the plane of polarization occurs when polarized light flows through a solution
containing only one of two optical isomers. The plane of plane-polarized light rotates clockwise
in one isomer. We refer to this as the + isomer. The other isomer, denoted as −, rotates the plane
of plane-polarized light in an anticlockwise direction. Equal concentrations of both optical
isomers in a solution cause the effects of polarized light to cancel out, making the solution
optically inactive. These kinds of solutions are said to contain a racemic mixture.
In order to obtain precise findings, chemists utilize a polarimeter, an apparatus that measures
rotations using monochromatic light, which is light with a single color or frequency.
1.6 Racemic mixture
A racemic mixture is a mixture of equal amounts of the two mirror-image forms of a chiral
compound. The mixture does not rotate polarised light because the two optical isomers have
equal and opposite effects so they cancel each other out.
An optically active compound's racemates, also known as racemic mixtures, are composed of
identical amounts of each enantiomer. Racemates exhibit no optical activity because the light-
rotating effects of the two enantiomers cancel each other out.
When two achiral substances react, chemists frequently obtain a racemic mixture of a chiral
product. This is due to the fact that each enantiomer typically has an equal chance of forming
when two molecules react.

1.7 A racemic mixture forms with reference to the nucleophilic addition mechanism.
A planar intermediate is created in the two-step SN1 mechanism following the first step. On the
other hand, there is an equal chance that the nucleophile will attack during the second step from
above or below the planar intermediate. The end result is a racemic mixture of the two forms of
the chiral alcohol, starting with one optical isomer of a halogenoalkane. According to Figure
below,, this indicates that the product is optically inactive.
The SN1 mechanism hydrolyzes an optically active halogenoalkane. The final product is a blend
of the alcohol's two optical isomers in equal proportions. This mixture is racemic.

21 Nitrogen Compounds
1.1 Formation of amines:
i.) reduction of a nitrile
Use a strong reducing agent, such as lithium aluminum hydride (LiAlH 4) in dry ether, to convert
a nitrile to an amine. Then, add some diluted acid.
The following is the equation for the conversion of ethanenitrile to ethylamine:

While this is fantastic in the lab, LiAlH 4 is too costly for widespread use. This process, known as
catalytic hydrogenation, is carried out by industry using a metal catalyst, such as platinum or
nickel, under high pressure and temperature.
ii.) reaction of NH3 with halogenoalkanes
Amines can be made by heating a halogenoalkane with excess ethanolic ammonia (ammonia
dissolved in ethanol).

Halogenoalkanes undergo a nucleophilic substitution reaction to form amines. This reaction's

general mechanism is as follows:
iii.) reduction of C6H5NO2 to C6H5NH2
Reducing a nitro compound, like nitrobenzene, yields aromatic amines. The method consists of
two steps: To make salt, a solution of concentrated hydrochloric acid, tin metal, and nitro
compound is heated under reflux. Next, an alkali is added to the mixture, such as sodium
hydroxide solution, to convert the salt into an aromatic amine.

1.2 Reactions of amines:

i.) with water
Ammonia acts as a Bronsted–Lowry base and a small proportion of the dissolved molecules
react with water to form a weakly alkaline solution containing hydroxide ions.
NH3(aq) + H2O(l) ⇋ NH4+(aq) + OH-(aq)
Butylamine and other amines act as Bronsted–Lowry bases in a similar manner by removing H +
ions from water molecules to form an alkaline solution containing hydroxide ions.

ii.) with acids

Amines react even more readily with acids than they do with water. The lone pair on the
nitrogen atom rapidly accepts an H+ ion from the acid to form a substituted ammonium salt.
C4H9NH2(g) + HCl(g) → C4H99NH3 +Cl−(s)
When the vapour of gaseous amines such as ethylamine reacts with hydrogen chloride gas, the
product, ethylammonium chloride, forms as a white smoke. The smoke settles as a white solid.
CH3CH2NH2(g) + HCl(g) → CH3CH2NH3 +Cl−(s)
iii.) with acyl chlorides
Amines also react as nucleophiles with the δ+ carbon atoms in acyl chlorides such as ethanoyl
chloride. The reaction forms an N-substituted amide.
1.3 The basicity of various aliphatic and aromatic amines.
Amines act as weak bases because they accept protons. There’s a lone pair of electrons on the
nitrogen atom that forms a co-ordinate (dative covalent) bond with an H+ ion

The availability of the nitrogen's lone pair of electrons determines the strength of the base. If its
electron density is higher, a single pair of electrons will be more available. The amine will be a
stronger base and more likely to accept a proton if the lone pair is more available. Weak bases
are principal aromatic amines. This occurs as a result of the nitrogen's lone pair partially
delocalized onto the benzene ring, which attracts electrons to itself. As a result, the nitrogen's
electron density drops. This makes the lone pair much less available. Primary aliphatic amines
are strong bases. This is because alkyl groups push electrons onto attached groups. So the
electron density on the nitrogen atom increases. This makes the lone pair more available. The
strength of ammonia as a base lies somewhere in between. This is because ammonia doesn’t
have an aromatic group to pull the lone pair of electrons away, or an alkyl group to push the
lone pair of electrons forward.

Diagram showing why primary aromatic amines are weaker bases than ammonia and why
primary aliphatic amines are stronger bases than ammonia.
1.4 Hydrolysis of amides under acidic and alkaline conditions.
Amphetidine hydrolysis In substituted amides, the two hydrocarbon sections of their molecules
are joined by the distinctive CONH group. Using an acid or an alkali to hydrolyze the link will
break it. To hydrolyze the amide, it is diluted with a solution of sodium hydroxide or
hydrochloric acid, for example:

A carboxylic acid (R1 COOH) and a primary amine (R2 NH2) are the byproducts of hydrolyzing a
substituted amide with acid. To create its ammonium salt, the amine will react with excess acid
in the reaction vessel, such as R2 NH3 + Cl− with excess hydrochloric acid. The products of an
alkali, like aqueous sodium hydroxide, are the primary amine (R2 NH2) and the sodium salt of
the carboxylic acid (R1 COO− Na+). The corresponding carboxylic acid and ammonia are the
products obtained from reacting an unsubstituted amide (RCONH2) with acid. An ammonium
salt is created when surplus acid and ammonia in solution [Link] products of an alkali are
ammonia and the salt of carboxylic acid.
1.5 IUPAC nomenclature of amines, amides and amino acids.
Using the IUPAC system, primary amines are named in two main ways. They are referred to as
alkanamines or alkylamines. The majority of primary amines that are joined to common names
linear alkanes, cycloalkanes, and alkyl groups are typically designated as [Link]
example the primary arylamine (C6H5NH2) is called aniline.
Amides are generally characterized by the bonding of a nitrogen atom to a carbonyl carbon
[Link] naming an amide, -amide is used in place of the common name's -ic acid or the
IUPAC's -oic ending for the corresponding carboxylic acid.
The IUPAC-IUBMB Joint Commission on Biochemical Nomenclature formally names amino acids
using the pseudo-"neutral" structure. For instance, alanine's systematic name is 2-
aminopropanoic acid, which is derived from the formula CH3−CH(NH2)−COOH.
1.6 General structure of amino acids.

The general structural formula of a 2-aminocarboxylic acid is RCH(NH2)COOH.

1.7 Amino acids have high melting points.
While alkyl amines and the small-chain aliphatic carboxylic acids are liquids, the amino acids
are all solids. They have high melting points (often decomposing before they can be heated to a
sufficiently high temperature to melt them), and are soluble in water. In another contrast to
amines and carboxylic acids, they are insoluble in organic solvents such as methylbenzene.
1.8 Structure of amino acid in acidic and alkaline solutions.
The large reduction in basicity and acidity is readily explained by the idea that the acidic and
basic groups within an amino acid molecule have already reacted with each other:

The product is an ‘internal salt’, called a zwitterion (from the German word Zwitter, meaning
‘hybrid’; zwitterionic structures were first proposed by the German chemist Küster in 1897). A
zwitterion is a molecule that contains both a cationic group and an anionic group.
1.9 The formation of zwitterions.
While amino groups are basic and draw hydrogen ions, carboxylic acid groups ionize and
produce hydrogen ions, H+(aq), in an aqueous solution. Because the amino groups take up
hydrogen ions, or protons, and the acid groups give them away, amino acids consequently form
ions in aqueous solution. But the peculiar thing about the formed ions is that they have both
positive and negative charges. Because the German word "zwitter" means "hybrid or
hermaphrodite," chemists refer to them as "zwitterions."
There is a pH at which an amino acid can only form zwitterions. A solution that is excessively
alkaline due to a high pH will have OH- ions that take away H+ ions from the zwitterions,
resulting in the formation of negative ions.
1.10 Zwitterion structures.

1.11 Structures of the di- and tri-peptides.

A combination of two or more amino acids can condense into an amide, which is what's known
as a peptide when it's formed from amino acids. A peptide is referred to as a dipeptide if it
consists of two amino acids.
If three amino acids join together, a tripeptide is formed.

1.12 Identification of amino acids after peptide hydrolysis using Rf values.

Since each amino acid has a unique "R" group, no two amino acids will dissolve in the same
solvent in the same way. This means that thin-layer chromatography (see Figure below) can be
used to quickly separate and identify the various amino acids present in a mixture.
With the chromatogram, we can determine the amino acids that are present in the mixture by
computing Rf values. This formula is used to determine the Rf value of each amino acid spot:
x distance travelled by spot
Rf = =
y distance travelled by solvent
Using a table of known amino acid Rf values, you can identify the amino acids in the mixture.
1.13 The purpose of ninhydrin in identifying amino acids in chromatography
experiments.
Amino acids are colorless; you must take an action to reveal them. The amino acids could turn
purple if you sprayed the plate with ninhydrin solution. As an alternative, you could use a
particular plate that has been treated with fluorescent dye. When exposed to UV light, the dye
glows.
Chemical spots on the plate cover the fluorescent dye, giving the appearance of dark spots. To
indicate the locations of the spots, place the plate under a UV lamp and draw around the dark
areas.
22 Condensation Polymers
1.1 Polyesters and polyamides as condensation polymers.
Condensation polymerisation
Condensation polymerization involves two methods. Every tactic produces a distinct kind of
polymer. In order to create type I polymers, the first strategy begins with a monomer that has
two distinct functional groups that can condense together to form amide or ester groups (see
Figure below).

The second strategy, which involves creating type II polymers, begins with two distinct
monomers, one of which has two groups of acyl chloride or carboxylic acid, and the other of
which has two groups of alcohol or amine (refer to Figure below).
1.2 Structure of polymers from the reactions of:
i.) dicarboxylic acids and diols

ii.) dicarboxylic acids and diamines

iii.) amino acids

1.3 Structure of repeating units of the following polymers:

i.) Kevlar
ii.) Nylon 6,6

iii.) Terylene

1.4 Repeating units from sections of a polymer.

A section of a polymer chain is shown below. Draw its repeating unit.

Starting from the first (CH2)2 , the repeating pattern goes to the second -NH-:

Move the -(CH2)2–NH- section from the start to the end, to get a C=O from an amide link at one
end and the corresponding -NH- at the other:
So the repeating unit looks like this:

1.5 Monomer(s) from a section of a polymer.

Identify the monomers that formed this condensation polymer:

This is a polyamide so if you remove the bond in the middle of the amide link you get:

Adding an OH group on to the C=O groups gives you: And adding a hydrogen on to each of the
NH groups gives you:

So these must be the monomers that joined to form the polymer.

1.6 The influence of intermolecular forces on the properties of polyesters and
polyamides such as Kevlar.
Kevlar's numerous regular hydrogen bonds between its chains are what give it its strength.
Kevlar's lengthy chains have a linear shape due to the 1,4-disubstituted configuration of the
functional groups in the two aryl rings. Strong interchain hydrogen bonds can be formed when
they easily align side by side.
The tensile strength of Kevlar is five times that of steel, on a weight-for-weight basis (its density
is small: about 1.5g cm–3), yet it is quite flexible. It finds uses in tyres for cars and bicycles,
bullet-proof vests and the ‘skins’ on modern drumheads.
1.7 Condensation polymers are classed as biodegradable.
Polymer biodegradability Chemically inert polyalkenes include poly(ethene) and polystyrene
(very unreactive). This is because nucleophiles cannot attack the non-polar bonds that hold the
repeating units together. When it comes to polymers, being chemically inert is advantageous (a
polystyrene cup won't react with your coffee, for example), but it also has a drawback in that it
prevents the polymers from degrading naturally because their bonds can't be hydrolyzed.
Hydrolysis is a method used to break down condensation polymers, such as nylon, a polyamide,
and PET, a polyester used to make, among other things, carrier bags and bottles for carbonated
drinks. This is because the bonds between the repeating units are polar and so are susceptible
to attack by nucleophiles such as water. Because the bonds in condensation polymers can be
hydrolysed, these polymers are biodegradable (they will break down naturally), although the
process is very slow.

23 Organic Synthesis
1.1 Synthetic routes up to four steps using any combination of reactions.
1.2 Drug synthesis often involves the production of a single optical isomer.
Nearly 90% of the most recent medications are marketed as racemates, which are composed of
an equimolar mixture of two enantiomers. Approximately half of the drugs currently in use are
chiral compounds. The majority of isomers of chiral drugs show notable differences in biological
activities, including pharmacology, toxicology, pharmacokinetics, metabolism, etc., despite
sharing the same chemical structure. Additionally, some of these properties' mechanisms are
[Link] order to remove the undesirable isomer from the preparation, find the best course
of action, and provide the patient with the appropriate therapeutic control, it is crucial to
encourage the chiral separation and analysis of racemic drugs in both the pharmaceutical
industry and the clinic. The nomenclature, pharmacology, toxicology, pharmacokinetics,
metabolism, and other aspects of a few common chiral drugs are reviewed in this article along
with their mechanisms. Examined are various methods for chiral separation employed in
clinical analyses and by the pharmaceutical industry.

1.3 Purification of an organic solid by recrystallisation.

Recrystallization is achieved by utilizing a solvent that dissolves the product when it is hot but
not when it is cold. Solvent selection is typically done through trial and error. Suction filtration
and the use of a Buchner or Hirsch funnel expedite the filtering process and make it easier to
remove the purified solid from the filter paper. The steps are as follows.
1 Use the smallest amount of hot solvent to dissolve the impure solid.
2 To eliminate insoluble contaminants, pass the heated mixture through a heated funnel if the
solution is not clear.
3 Lower the temperature of the filtrate until the product recrystallizes, leaving the less soluble
impurities in solution.
4 Recover the purified product by filtering.
5 Remove any impurity-containing solution from the purified solid by washing it with tiny
volumes of cold, pure solvent.
6 Put the purified solid in a desiccator or let the solvent evaporate from it naturally.
1.4 Melting point of an organic solid as an indicator of purity.
Impure solids soften and melt over a wider temperature range than pure solids, which have
sharp melting points. Thus, observing a solid melt can frequently reveal the purity of the
material. Since databases now contain the melting points of every known compound, one can
verify a product's identity and purity by observing that it melts quickly at the predicted
temperature (Figure below).

24 Analytical Techniques (mass spectroscopy, infra-red spectroscopy, NMR spectroscopy

and chromatography)
1.1 Identification of the molecular ion peak in a mass spectrum.
In a high resolution time of flight mass spectrometer, a combination of two compounds was
analyzed. The spectrum below displays the two molecular ion peaks that were produced by the
sample.
1.2 The use of m/z values of fragment peaks to identify an organic compound.
The mass spectrum indicates the presence of isotopes. For example, nearly equal amounts of the
isotopes 79Br and 81Br are found in bromine. There are two molecular ion peaks with nearly
equal abundances at m/z = 108 and 110 in the bromoethane spectrum.

The process of breaking the C-Br bond to produce the fragment ion C 2H5+ with m/z = 29 is the
first step in the fragmentation of either molecular ion. The formation of ions from additional
successive losses of hydrogen atoms results in the peaks at m/z = 28, 27, and 26.

1.3 Use of infra-red spectra and data from the data book to identify functional groups.

Bond Frequency of absorption

(wavenumber)/cm−1
 C-H 2800–2900

C=C 1650

C=O 1715

O-H (alcohol) 3200–3500

O-H (carboxylic acid) 1720

1.4 The use and limitations of the fingerprint region (0-1500 cm−1) in infra-red
spectroscopy.
The fingerprint region is the complex region of the spectrum below 1500cm−1 which contains
many single bond stretching and bending vibrations and is unique to each molecule.
It is possible to compare an unknown compound's complex pattern with stored infrared spectra
in a database. The unknown compound will be identified by an exact match.
One analytical tool that can be used to track the development of an organic synthesis is infrared
spectroscopy. To determine whether a product is pure, its spectrum should be compared to a
known spectrum stored in a database.
1.5 13C NMR spectra to identify: i.) different carbon environments from the chemical shift
ii.) possible structures of organic compounds
Carbon-13 NMR relies on the magnetic properties of the 13C isotope. This isotope makes up
only about 1% of all naturally occurring carbon atoms, but this is enough for a signal to be
detected in an NMR machine.

The 13C NMR spectra of ethanol shows two peaks. This illustrates the reality that an ethanol
molecule contains two carbon atoms, each of which is located in a distinct environment. Three
hydrogen atoms and a carbon atom are joined by the carbon in the CH 3 group. Two hydrogen
atoms, a carbon atom and an oxygen atom, are joined by the carbon in the CH2 group.
Typically, the sample is recorded in solution to obtain spectra similar to the ones displayed in
Figure above. A typical solvent selection is CDCl3. Since CDCl3 molecules only have one carbon
atom, their 13C spectra only show one distinct line.

1.6 The use of structures to predict the following in 13C NMR spectra: i.) number of
environments ii.) chemical shifts of different carbon environments
Figure below illustrates the principles of 13C NMR in a more complex example. Here, too, every
carbon atom, or group of carbon atoms, in a chemically distinct environment gives a separate
peak in the NMR spectrum.

4-methylpentan-2-one has six carbon atoms, but the 13C NMR spectra shows only five peaks. An
illustration of this can be found in Figure below. Only one peak is produced by the carbon atoms
of the two methyl groups in the molecule because their environments are identical. The
environments of the other four carbon atoms, including the one in the third methyl group, are
marginally different and result in distinct peaks.
1.7 1H NMR spectra to identify: i.) different hydrogen environments from the chemical
shift ii.) number of hydrogens from relative peak areas
The main focus of 1H NMR is the response of hydrogen nuclei to a magnetic field.
One proton makes up an atom's nucleus in hydrogen. Hence, 1H NMR is also referred to as
"proton NMR," and the hydrogen atoms involved may be referred to as "protons" in this context.
Similar to a 13C NMR spectrum, which indicates the number of distinct carbon environments,
each peak on a 1H NMR spectrum is caused by one or more hydrogen nuclei (protons) in a
specific environment. However, the relative area under each peak in 1H NMR also indicates the
relative quantity of H atoms in each environment.

There are two peaks so there are two hydrogen environments. The numbers above the peaks
tell you the area ratio between the hydrogens in each environment, which here is 1 : 3 so there’s
1 H atom in the environment at d = 11.5 ppm to every 3 H atoms in the other environment.
iii.) number of adjacent hydrogens from splitting patterns and the n+1 rule iv.) possible
structures of organic compounds
Because there is one hydrogen atom on the nearby carbon atom, the peak caused by the purple
hydrogens is divided into two parts. Because there are two hydrogen atoms on the nearby
carbon atom, the red hydrogen peak is divided into three parts. The ratio of hydrogens in the
red environment to those in the purple environment is 1:1, as indicated by the numbers above
the peaks.
1.8 The use of structures to predict the following in 1H NMR spectra: i.) number of
environments ii.) chemical shifts of different hydrogen environments iii.) relative peak
areas iv.) splitting patterns

The areas beneath the three peaks correspond to the number of protons in each chemical
environment and are in the ratio 2:3:3. The relative area under each peak is occasionally
indicated on published NMR spectra by a number above the peak, as Figure below illustrates.
Peaks A and C appear to be multiple peaks at higher resolution, while peak B stays single. This is
due to interactions between the nuclear spins of the protons in the ethyl group, which are in
charge of peaks A and C.
1.9 i.) the use of TMS (tetramethylsilane) in NMR
The sample is dissolved in a solvent for NMR spectroscopy. Tetramethylsilane (TMS), a standard
reference compound that generates a single, sharp absorption peak far away from the peaks
produced by the samples for analysis, is also present in the solution.
One or more magnetic atoms in a specific chemical environment are represented by each peak.
In an NMR machine, the magnetic fields that are applied to nuclei in different parts of a molecule
vary slightly. This is due to the fact that they are partially or completely shielded from the
spectrometer's applied field by the tiny magnetic fields resulting from the electrons in nearby
bonds and atoms.
The recorder outputs a computer-analyzed spectrum with peaks located in the areas where the
sample absorbs radiation most intensely. The absorption of magnetic atoms in the reference
chemical fixes the zero on the scale. "Chemical shifts" refers to the sample peaks' separations
from this zero. δ is the symbol for chemical shift.
ii.) the use of deuterated solvents such as CDCl3
Given its low boiling point, which facilitates simple sample recovery, and its lack of chemical
reactivity and low likelihood of exchanging deuterium with its solute, deuterated chloroform is
a versatile NMR solvent.
Since CDCl3 molecules only have one carbon atom, their 13C spectra only show one distinct line.
To prevent confusion, this line is typically removed from the spectra in databases like SDBS.
None of the 13C spectra display the line that the solvent produced.
1.10 The use of D2O to identify O-H and N-H protons in 1H NMR.
In an NMR spectrum, protons that are directly bonded to oxygen or nitrogen atoms can show up
practically anywhere. The solution's capacity to form hydrogen bonds and acidity determine the
resonance field strength. These protons frequently do not split the peaks of adjacent protons
due to easy proton exchange with other O-H or N-H protons in the sample. Deuterium exchange,
however, can be used to distinguish them.
Protons are exchanged with deuterium atoms in D2O (also known as "heavy water," D = 2H)
when the compound containing them dissolves in it. Since deuterium atoms have an even
number of nucleons, their peaks do not resonate, and the peaks caused by the OH or NH2
protons vanish:
1.11 Basic principle of chromatography in terms of mobile and stationary phases.
Chromatography is used to separate and identify chemicals in mixtures.
Chromatography is a useful technique for separating components out of mixtures, allowing for
easy component identification. Chromatography comes in a wide variety of forms, but they all
share the same fundamental configuration:
A mobile phase: where the molecules can move. This is always a liquid or a gas.
A stationary phase: where the molecules can’t move. This must be a solid, or a liquid on a solid
support.
They both employ the same fundamental idea. The stationary phase is traversed by the mobile
phase. More soluble components in the mobile phase will travel farther than more strongly
adsorbed (attracted) components to the stationary phase. The amount of distance that each
substance travels is determined by its solubility in the mobile phase and its retention by the
stationary phase. These variations in solubility and retention are what set the various
substances apart.
1.12 Rf values from thin layer chromatograms.
A sugar solution containing a mixture of three sugars is separated using TLC. The
chromatogram is shown on the right. Calculate the Rf value of spot X. To find the Rf value of spot
X all you have to do is stick the numbers into the formula:

distance travelled by solvent

Rf value=
distance travelled by solvent

= 2.5 cm ÷ 10.4 cm = 0.24

1.13 Comparision between the gas chromatography and HPLC (High Performance Liquid
Chromatography) in terms of:
i.) mobile and stationary phases
Partitioning is a technique used in high-performance liquid chromatography, or HPLC, to
separate and identify the constituents of a mixture. A nonvolatile liquid, like a long-chain
hydrocarbon liquid, is bonded to a solid support, like tiny silica particles, to form the stationary
phase. It is firmly arranged in a column. A polar solvent, such as a methanol/water solvent, is
typically selected for the mobile phase. The material needs to be pushed through the tightly
packed column where separation happens while under pressure.
Similar to HPLC, gas chromatography (GC) involves the introduction of a gaseous sample into
the column. An inert carrier gas is used to transport the sample through the stationary phase,
which is contained in the column. This technique works with volatile solids (since they have to
be in the form of a vapour), gases, and liquids.
ii.) limitations and uses
HPLC is used in the following applications: monitoring pollutants in the atmosphere and rivers,
such as measuring pesticide levels; separating peptides and proteins in medical research;
analyzing urine samples from athletes for prohibited substances like steroids or stimulants; and
by food standards agencies verifying the accuracy of the information on food labels.
Gas chromatography is used for the following purposes: determining the amount of alcohol in
driver blood samples; monitoring the presence of chemicals in industrial processes; identifying
pesticides in river water; tracking down the source of oil pollution from the pattern of peaks,
which functions as a fingerprint for any batch of oil.
1.14 Retention time.
The retention time in gas chromatography is the time it takes for a compound in a mixture to
pass through a chromatographic column and reach the detector.
The duration required for a compound to pass through the column is indicated by the peak's
position on a GC printout. This is known as the retention time of the compound.
The relative amounts of each compound in the mixture are indicated by the area under each
peak. Measuring the peak heights is sufficient to determine the relative amounts if the peaks are
narrow.
Capillary columns are found in some GC instruments. These have an extremely small internal
diameter and are 20–60 meters long. Silica with an outer polymer coating is commonly used to
make capillary columns. The interior surface of the column, which adsorbs chemicals to varying
degrees, is the stationary phase.
Coating the inner surface is an option.
1.15 Chromatograms to identify the percentage composition of a mixture.
The area of each component peak is measured after the component peaks have been identified
for quantitative [Link] peaks' approximate triangular shape means that their area is:
½ × base × height (i.e. the area of a triangle)
The GLC apparatus can print the results along with the chromatogram and typically measures
the peak's area automatically. Peak height can be used to estimate the proportion of
components in a mixture instead of peak area if the peaks are very narrow or have similar base
widths.
For this method, all of the mixture's components must be separated, the chromatogram must
display peaks for each component, and the detector's response to each component must be
equal so that the peak area is directly proportional to the component concentration.
Each component's amount in a mixture can be calculated by expressing it as a percentage of the
total area under all of the peaks. For instance, if three esters, A, B, and C, are mixed together:
peak area(¿ h eig ht ) of A
(¿ .)% of ester A= × 100
∑ of t h e areas (¿ h eig hts)of A , B∧C
1.16 Mass spectrometry can be used alongside gas chromatography to help identify
components in a mixture.
A method for identifying substances based on their mass/charge ratio is spectrometry. Although
it is excellent at identifying unknown compounds, a mixture of substances would yield
confusing results. Conversely, gas chromatography (refer to the previous page) excels at
dissecting a mixture into its constituent parts but struggles with component identification.
Combining these two methods yields an incredibly helpful analytical tool. The advantages of
mass spectrometry and gas chromatography are combined to create a powerful analytical tool
known as gas chromatography-mass spectrometry, or GC-MS.
Gas chromatography is used to separate the sample; however, the separated components are
fed into a mass spectrometer rather than a detector (see Figure below). Every component that
the spectrometer creates has a mass spectrum that can be used to identify it and determine the
composition of the original sample. The entire procedure can be automated by using computers
to compare the mass spectrum of each mixture component to a database.

This method has an advantage over standard GC in that it allows for the positive identification of
the components that the chromatography separated out, something that may not be possible
from a chromatogram alone (since similar compounds frequently have very similar retention
times).