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A Level.

Chemistry (9701)

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Chapter 1 (AS-Level)
Atomic Structure Discovering the electron
A. Study of Cathode rays
At normal pressures, gases are poor conductors, but at lower pressure they become better conductors of electricity. Scientists studied the effects of passing electricity through gases at low pressures. A scientist named William Crookes saw that the glass of the containing vessel opposite the cathode glowed when the voltage applied was high. A solid object placed between the cathode and the glass causes a shadow. They proposed that the glow was caused by rays coming from the cathode, called cathode rays. There was some argument about whether the rays are waves or particles. The most important evidence is that they are deflected by magnetic fields, which is best explained by assuming that these are electrically charged particles.
The direction of deflection, which is towards the positive pole shows that they are negatively charged.

B. J.J. Thomsons e/m experiment


J.J. Thomson measured the deflection of a narrow beam of cathode rays in both magnetic and electrical fields. His results allowed him to calculate the charge-to-mass ratio (e/m) of the particles. Their charge-to-mass ratio was found to be exactly the same, whatever gas or types of electrodes were used in the experiment. The cathode ray particles had a very small mass, 1/2000 of a hydrogen atom. He decided to call them the electrons. The name was suggested by George Johnstone Stoney for the units of electricity.

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C. Millikans Oil drop experiment


The electron charge was first measured by the American Physicist Robert Millikan using his Oil drop experiment. He gave the oil drops negative charge by spraying them into air ionized by Xrays. He adjusted the charge on the plates so that the upward force of attraction equaled the downwards force of gravity, and so the drop would stay stationary. Calculations on the forces allowed him to find the charges on the drops. These were multiples of the charge on an electron. He found that the electron had a charge of 1.602 x 10-19 C (coulombs). They had a mass of 9.109 x 10-31 kg, which is 1/1837 of the mass of a hydrogen atom.

Discovering the protons and neutrons


The new atomic models; the Plum-Pudding, and the Nuclear Atom
New discoveries needed new atomic models. If there are negatively charged electrons in all neutral atoms, then there must be a positively charged particle to cancel them out. For some time, the most favored was the J.J. Thomsons Plum-Pudding model, in which the electrons were embedded in a pudding of positive charge. Then an experiment in 1909, by Hans Geiger and Ernest Rutherford, changed everything. They were investigating how alpha particles were scattered when they were fired at very thin sheets of different metals. They detected alpha particles by flashes of light that were caused by the impact with a fluorescent screen. Some, however, were deflected with large angles.

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The Plum-Pudding model couldnt explain the surprising observations. However, Rutherford suggested that atoms consist of largely empty space and that the mass is largely concentrated into a very small, positively charged nucleus.

Most alpha particles pass through the empty space in the atom with very little deflection. When the alpha particle approaches on a path close to the nucleus, however, the positive charges strongly repel each other, and the alpha particle is deflected through a large angle.

Particles in the nucleus


The proton

Rutherford reasoned that there must be particles that are responsible for the positive charge. He and Marsden fired alpha particles through hydrogen, nitrogen and other elements. They detected new particles with positive charge and the approximate mass of a hydrogen atom. He called these particles protons. The proton has a positive charge of 1.602 x 10 -19 C, equal in size but different in charge of that of an electron. It has a mass of 1.673 x 10-27 kg. Each electrically neutral atom has the same number of protons as the number of electrons outside the nucleus.
The neutron

The mass of the atom, which is concentrated in its nucleus, cannot depend only on protons, as they usually provide around half of the atomic mass. Rutherford then proposed that there is another particle in the nucleus which has the same mass of the proton but with no electrical charge. As the particle is not charged, its detection was very difficult, not until 1932. One of his co-workers, James Chadwick, produced sufficient evidence for the existence of the neutron.

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Using the apparatus Chadwick bombarded a block of beryllium with alpha particles. No charged particles were detected on the other side of the block. However, when a block of paraffin wax was placed near the beryllium, charged particles were detected and identified as protons. The alpha particles had knocked out neutrons from the beryllium, and in turn these knocked out protons out of the wax.
Order of discovery of subatomic particles 1. Electrons (cathode ray) 2. Protons 3. Neutrons (1932)

Atomic and Mass numbers

Atomic Number (Z)


The difference between atoms of different elements is the number of protons in the nucleus of each atom. The atomic number shows: The number of protons in the nucleus The number of electrons in a neutral atom of that element The position of the element in the periodic table

Mass number (A)


It is useful to have a measure for the total number of particles in the nucleus of an atom. It is called the mass number. For any atom: The mass number is the sum of the number of protons and the number of neutrons in the nucleus

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Behavior of protons, neutrons and electrons in electric fields


The three particles behave differently in electric fields due to a different charge on them and their relative masses. Protons are attracted to the negative pole and electrons are attracted to the positive pole. Because electrons are much lighter, they are deflected more.Neutrons are not deflected as they have no charge on them. Summary: Particle Name Relative Mass Relative Charge Proton Neutron Electron 1 1 negligible +1 0 -1

Isotopes
In Rutherfords atomic model, the nucleus consists of protons and neutrons, each with a mass of one atomic unit. The relative atomic masses of elements should then be whole numbers. It was a puzzle why chlorine has a relative atomic mass of 35.5. The answer is that atoms of the same element are not all identical.
These atoms that have the same proton number but a different mass number are called isotopes.

For example, hydrogen has three isotopes: Isotope Symbol Protium Deuterium Tritium

Protons Neutrons

1 0

1 1

1 2

Electrons in atoms
The electrons are involved in the changes that happen in chemical reactions, so if we knew everything about the arrangements of the electrons in atoms and molecules, we could predict most of the ways that chemicals behave, purely from mathematics.

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There are some models that show how the electrons are arranged around the nucleus. The first and most simple one is that thy orbit the nucleus which was rejected. This is because the electrons would soon lose energy and fall down into the nucleus. The second model is that they orbit around the nucleus, in shells or energy levels.

Arrangement of electrons: Energy levels and shells


In 1913, a Danish physicist Niels Bohr proposed his ideas about arrangements of the electrons in atoms. The German physicist Max Planck had proposed in his Quantum Theory, that energy is atomic, and can only be transferred in packets, or quanta. Bohr applied this theory to the energy of electrons. So he suggested that electrons can only have energy in quanta, and so they can only exist in quantized levels of energy. If an electron gains or loses energy, it will travel up and down the energy levels, respectively, but cannot stay somewhere in between. These energy levels are most commonly called as shells. Shells are numbered 1, 2, 3, 4, etc. These numbers are known as the principal quantum numbers, which are given the symbol n. Such numbers correspond to the periods in the periodic table. For a given element, electrons are added to the shells as follows: Up to 2 in shell 1 Up to 8 in shell 2 Up to 18 in shell 3

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Ionisation energy
When an atom loses an electron it becomes a positive ion. We say that it has been ionized. Energy is needed to remove electrons and this is generally called Ionisation Energy.
The first ionisation energy of an element is the amount of energy needed to remove one electron from each atom in a mole of atoms of an element in the gaseous state.

The general symbol for ionisation energy is Hi and for the first ionisation energy it is Hi1. X(g) X+(g) + e1M 1M

2nd Ionization Energy/Enthalpy/Potential X+(g) X2+(g) + e1M 1M

3rd Ionization Energy/Enthalpy/Potential X2+(g) X3+(g) + e1M 1M

Examples of ionisation energies of the element Nitrogen: Electrons removed N 1 2 3 4 5 6 7

1400

2860

4580

7480

9450

53300

64400

Trends in Hi (Ionization energy):


1) HI increases as more and more electrons are removed i.e. HI2 > HI1. 2) There are one or more particularly large sizes of HI within the successive HI of each element (except for H and He), due to the jump from one energy level to another.

Factors affecting HI:


1) The size of the positive nuclear charge; the greater the positive nuclear charge the greater the HI. 2) The distance of electrons from nucleus; the further the e- is from the nucleus, the weaker the attraction and therefore the smaller the ionization energy needed. 3) The shielding effect of inner electrons; as the number of inner shells increases, the HI decreases.

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In general: 1. As we go from left to right across a period, the nuclear charge increases and atomic size decreases, HI increases. 2. As we go down a group the shielding effect and atomic size increases and HI decreases.

HI increases

(Periodic table)

HI decreases

3. Electrons are in discrete energy levels (quantized) (or shells) characterized by their principal quantum numbers (n= 1,2,3,4, etc) 4. The nearest to the nucleus is shell K with n=1, the next is L with n=2. The furthest away from the nucleus has the highest energy (energy becomes higher)(less negative) 5. The maximum number of electrons in an energy level (or shell) is given by the equation #e = 2n2 where n is principal quantum number

Need for a more complex model


The electronic configurations are not so simple. For some elements, like lithium to neon, their first ionization energies dont increase evenly. This, and other complications, shows the need for a more complex model of electronic configurations, other than the Bohrs model.

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Bohrs model as shown by quantum mechanics:


1) Energy levels consist of one or more sublevels which contains orbitals at different energies. 2) Sublevels are s, p, d, f types S contains one orbital P contains three orbitals D contains five orbitals F contains seven orbitals. 3) An orbital is a region in space around the nucleus where there is a high probability of finding a particular electron. 4) Orbitals have different 3D shapes, no exact boundaries. They are fuzzy like clouds, often called electronic clouds, drawn with boundaries to represent 90-95% of the space in which an electron exists. 5) S orbitals are spherical 6) While P orbitals are dumbbell shaped with 2 lubes extending along X, Y and Z axes.

Filling the orbitals and electronic configurations


Three important rules: 1) Pauli Exclusion Principle. - Any orbital cannot hold more than 2 electrons, in this case they should be paired (spin-paired) 2) In filling shells and orbitals, the orbitals of the lowest energies are filled first. (i.e. the electronic configuration [distribution of electrons] should be given in its lowest energy state. 3) Orbitals of equal energies (degenerate orbitals) are filled singly first. Then you should double up with more electrons. (Lowest energy state = Ground state)

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Examples of electronic configuration of some elements:

First 18 elements:
1 1 3 4 5 6 7 8 9 10 H He Li Be B C N O F Ne 1s1 1s2 1s2 2s1 1s2 2s2 1s2 2s2 2p1 1s 2s 2p
2 2 2

Electronic configuration for some of the elements from 19 to 36:


19 K 20 Ca 21 Sc [Ar] 4s1 [Ar] 4s2 [Ar] 3d1 4s2 24 Cr [Ar] 3d5 4s1

1s2 2s2 2p3 1s2 2s2 2p4 1s 2s 2p


2 2 5

25 Mn [Ar] 3d5 4s2 29 Cu 30 Zn 31 Ga [Ar] 3d10 4s1 [Ar] 3d10 4s2 [Ar] 3d10 4s2 4p1
1

1s2 2s2 2p6

11
12 13 14 15 16 17 18

Na
Mg Al Si P S Cl Ar

1s2 2s2 2p6 3s1


1s2 2s2 2p6 3s2 1s 2s 2p 3s 3p
2 2 6 2

35 Br 36 Kr

[Ar] 3d10 4s2 4p5 [Ar] 3d10 4s2 4p6

1s2 2s2 2p6 3s2 3p2 1s2 2s2 2p6 3s2 3p3 1s2 2s2 2p6 3s2 3p4 1s2 2s2 2p6 3s2 3p5 1s2 2s2 2p6 3s2 3p6

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Some electronic configurations arrow in box form:

1s H

2s

2p

He

Li

Ne

4s K [Ar]

3d

4p

Sc

[Ar]

Mn

[Ar]

Ga

[Ar]

Kr

[Ar]

END OF LESSON

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Chapter 2
Atoms, molecules and Stoichiometry Counting atoms and molecules
There are two important definitions to remember in this chapter: Relative Atomic Mass, Ar, or an element: o Average mass of one atom relative to the mass of one atom of C12 which is considered to be 12 (atomic mass unit A.M.U) Relative Isotopic Mass of an Isotope of an element: The mass of one atom of the isotope relative to that of one atom of C12. To calculate the Ar of an element we have to consider all the isotopes of the element and their abundance. = ( %) Example, to find the relative atomic mass of chlorine: Isotopes: Chlorine-35, abundance = 75.5% Chlorine-37, abundance = 24.5% Therefore: =( = The mass of different molecules are compared in a similar fashion. The relative formula mass (Mr) of a compound, is the mass of a molecule of the compound relative to the mass of an atom of carbon-12. To find the relative Mr of a compound, we add up all the Ars of the elements in the compound. Example for CH4: = = ( ) )

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Determination of Ar from mass spectra
Ar is determined using an instrument called the mass spectrometer. The instrument is shown below:

Knowledge of the working of the mass spectrometer is not required by CIE. The results of the mass spectrometer would be shown on a computer screen, as a chart of abundance against mass. For example, for zirconium:
60

ex: Zirconium
50 % Age Abundance

40
30 20 10 0 90 91 92 93 94 95 96 Mass/charge ratios (m/e)

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Counting chemical substances in bulk
The mole and Avogadros constant
A mole of atoms is a quantity that contains Avogadros number (61023) of atoms.

Similarly, A Mole of molecules: o It is a quantity of the substance contains Avogadros number of molecules. (e.g. : a mole of ions a electrons)
In terms of mass, A mole of atoms is a quantity in grams equal to the relative atomic mass.

that

mole of

For example, 1mol of S atoms weighs 32 grams.


Relative Molecular Mass (Mr) is the sum of atomic masses of all atoms in the molecule.

Examples are found in the book.

The empirical (simplest) formula & molecular formula:


The Empirical Formula: Of a compound shows the simplest whole-number ratio of the elements in the compound The Molecular Formula: Of a compound shows the real number of each element in a molecule of a compound. Example 1: SAQ 2.10 pg21
Q: Copper oxide has the following composition by mass: Cu = 0.635g ; O = 0.08g. Calculate empirical formula of the oxide: ANS: Ar (Cu) =63.5 Cu Ar (O) =16 O

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2 Cu2O

Combustion analysis
The composition by mass of organic compounds can be found by combustion analysis. This involves the complete combustion in oxygen of a sample of a known mass. In combustion analysis, all the carbon is converted to carbon dioxide and all the hydrogen into water. These produced are carefully collected and weighed. Calculation gives the mass of carbon and hydrogen present. If oxygen is also present, its mass is found by subtraction (elimination). Other elements require other methods. mass of C in a sample = mass of CO2 mass of H in a sample = mass of H2O

Example: SAQ 2.11 pg22


Q: On complete combustion of 0.4g of a hydrocarbon (only H and C), 1.257g of CO2 and 0.514g of H2O were produced.

a) Find the Empirical formula of the hydrocarbon ANS: Find C: 1.257 C = 0.3428g Find H: 0.514 H = 0.0571g

= 0.02856 =1 CH2

= 0.0571 =2

b) If relative molecular mass of the hydrocarbon is 84, what is its molecular formula

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ANS: mass of CH2 = 14 =6 So, the molecular formula is C6H12

Calculations involving reacting masses:


Fe2O3 + 3CO 2Fe + 3CO2 - molar mass of Fe2O3 = (256) + (316) = 160 g/mol - one mole of Fe2O3 gives 2 moles of Fe. 160g of Fe2O3 gives (256) = 112g of iron 1000g of Fe2O3 gives 112 Example 1: SAQ 2.8 pg20 QUE: Calculate the mass of iron produced from 1000 tons of Fe2O3. How many tons of Fe2O3 would be needed to produce 1 ton of iron? If the iron ore contains 12% of Fe 2O3, how many tons of ore are needed to produce 1 ton of iron? ANS: 1) 1,000,000,000g of Fe2O3 gives 112 2) 112 3) 1.43 = 1,000,000, = 11.9 tons x = 1.43 tons = 700,000,000g = 700 tons = 700g of iron

Calculations involving concentration:


Concentration is how much solute is available in a specific volume of solution. Concentration by Mass: o how many grams of solute in 1 dm3 solution. (unit is g/dm3) (m/v) Concentration by Moles (Molar concentration): o How many moles of solute in 1 dm3 solution (unit is moles/dm3 (n/V)

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Example 1:
QUE: What amount of NaOH is present in 24.0cm3 of an aqueous 0.010 mol/dm3? ANS: Convert the volume to dm3 1dm3 = 10 10 10cm3 = 1000cm3 24.0 cm3 = dm3 0.010mol

Amount of NaOH in 24.0cm3 =

= 2.40 10-4mol

Calculations involving gas volumes:


Equal volumes of different gases contain the same number of molecules under same conditions of temperature and pressure, and this number is Avogadros Number. The opposite is also true, equal numbers of molecules of different gases, under same conditions of temperature and pressure occupy the same volume. At room temperature and pressure (r.t.p), one mole of any gas occupies approximately 24dm3 (at s.t.p, this is 22.5dm3).Reacting volumes of gases under same conditions of temperature and pressure can be used to determine the formula and stoichiometry of reaction. Example 1: QUE: 10cm3 of hydrocarbon burned completely in 50cm3 of oxygen produced 30cm3 of CO2 at r.t.p. Determine the formula of hydrocarbon and write a balanced equation of the reaction. ANS: HC(g) Volume: 10cm3 / 10 1 1 : + O2 (g) 50cm3/10 : 5 5 CO2 (g) + 30cm3/10 : : H2O(l) 3 3

Gas Volume Ratio: Gas Mole Ratio:

3 moles of C come from 3 moles of O2 react with 3 moles of CO2 5-3 = 2 moles of O2 which react with hydrogen 4H2 + 2O2 4H2O 2 moles of O2 react with 8 moles of H atoms, which gives C3H8

C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O

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Example 2: SAQ 2.21 pg27 QUE: 20cm3 of gaseous hydrocarbon Y burned completely in 60cm3 of oxygen to produce water and 40cm3 of CO2 (@ r.t.p) a) What is formula of hydrocarbon Y b) Write a balanced equation for the reaction. ANS: HC(g) + O2 (g) CO2 (g) + H2O(l) Volume: 20cm3 60 cm3 : : 3 3 40 cm3 : : -2 2 6-4= 2 moles to react with H2 C 4H8/2 gives C2H4 + 3O2 2CO2 + 2H2O

Gas volume ratio: 1 Gas mole ratio: 1

4C + 4O2 4 moles of Co2 8H + 2O2 4H2O

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Summary:
Relative Atomic Mass, Ar, or an element is the average mass of one atom relative to the mass of one atom of C12 which is considered to be 12 (atomic mass unit A.M.U).

Relative Isotopic Mass of an Isotope of an element the mass of one atom of the isotope relative to that of one atom of C12.

= ( %)

A mole of atoms is a quantity that contains Avogadros number (61023) of atoms.

Relative Molecular Mass (Mr) is the sum of atomic masses of all atoms in the molecule

The Empirical Formula of a compound shows the simplest whole-number ratio of the elements in the compound

The Molecular Formula of a compound shows the real number of each element in a molecule of a compound.

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Chapter 3 (AS-Level)
Chemical bonding and structure A. Covalent bonding
Simple molecular
Liquids and gases Low melting solids H2O, NH2, C2H5OH, Sucrose

Properties: A. Low boiling point and melting point B. Nonconductors of electricity C. May be insoluble in H2O, may dissolve in organic solvents

Giant molecular
Solids of high melting point and boiling point Quartz

Properties: A. High boiling point and melting point B. Nonconductors C. Insoluble in H2O and other solvents

In covalent bonds, electron pairs are shared between atoms. The electron pairs lying between the two nuclei are attracted by both nuclei, thus bonding them and thus overcoming the repulsion between them. In covalent compounds, the shared electron pairs are in molecular orbitals rather than atomic orbitals
Molecular Orbitals arise from the overlap of atomic orbitals.

Atomic Orbitals s, p, d H C=C H H


Examples of simple covalent molecules:

Molecular Orbitals H , ,

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Molecular formula Cl2 Structure Bonds

Cl-Cl

CH4

H2O

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NH3

C2H4

CO2

O=C=O

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Dative covalent (coordinate) bond:
A lone pair from one atom overlaps with an empty orbital in another atom. Ex: +

NH3 + [H] + H H N H + H H N H
Ex: Al2Cl6

Cl

Cl

Cl

Al

Dative covalent bond

Al

Cl

Cl

Cl

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B. Bonds of intermediate (in between covalent & ionic) character
Ionic, of covalent character:
Polarization of Ions: These are ionic compounds that show some properties which are more characteristic of covalent compounds. These ionic compounds contain anions which have become polarized.

1) Polarization of anion is the distortion of electronic cloud by the cation. 2) Polarization brings more electron charge between the two ionic nuclei producing a certain degree of covalent bonding. 3) Distortion:

purely ionic

partial ionization

extensive Ionic Molecule of Covalent Character

4) Cations with smaller radius and greater charge (i.e. greater charge density) have greater polarization on anions. 5) Anions with larger radius and greater charge are more easily polarized by cations.

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Covalent, of ionic character
Polarity of Covalent Bond

1) Covalent bonds in molecules become polar if there is difference in electronegativity between the elements. EN is the ability to attract the shared e-pairs. EN increases Most EN

Least EN Periodic Table (F>O>N>Cl) Most electro-negative

2) The more electronegative atom attracts the shared pair(s) more to itself leading to formation of a dipole. (i.e. ionic character). 3) In polyatomic molecules, the shape of the molecule must be taken into account.
Diatomic and polyatomic molecules

Diatomic

To predict the polarity in a molecule, the molecular shape should be known

Polyatomic

Non-polar, the 4 polar bonds cancel each other out.

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Shapes of simple molecules:
We apply VSEPR (Valency Shell Electron-Pair Repulsion Theory). Bonding and non-bonding e-pairs repel each other. The repulsion causes these pairs to move as far apart as possible. The orientation in space of these pairs determines the shape of the molecule. CH4 (tetrahedron)

NH3 (trigonal pyramidal)

Lone pair

SO42- ion

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H2O (V-shaped)

CO2 (linear)

BF3 (trigonal planar)

SF6 (octahedral)

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Summary:
1) Simple Molecules, central atom has no LPs Formula AB2 AB3 AB4 AB5 AB6 Shape linear trigonal planar tetrahedral trigonal bipyramidal octahedral 2) Simple Molecules, central atom has LPs Formula AB2 AB2 AB3 # of LPs 1 2 1 Shape V-shaped V-shaped trigonal pyramidal

Lone pairs, bonding-pairs and bond angles: Lone-pairs , Bonding-pairs , Bond Angles

LPs occupy bigger space than BPs LP-LP > LP-BP > BP-BP

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Bond length and bond enthalpy:
Single Bond Length > Double Bond Length > Triple Bond Length Bond Enthalpy: energy required to break 1 mol of given bond in 1 mol of gaseous molecules. Single Bond Enthalpy < Double Bond Enthalpy < Triple Bond Enthalpy

C. Metallic bonding
Properties of Metals: Shiny Good conductor of electricity & heat in solid state Sonorous Ductile Malleable

Bonding: In metallic bonding (lattice), the atoms lose their electrons (outer-shell), which extend throughout the lattice, thus forming a sea of electrons surrounding a lattice of positive ions. Metallic bonding explains the properties of metals.

Intermolecular forces:
Instantaneous dipole, induced dipole (van der waals forces)
Present in atoms and non-polar molecules.

He

He

attraction of + to - charge

Ex: noble gases, alkanes, polymers like LDPE & HDPE.., graphite Gases: Cl2 Liquids: Br2 Solids: I2

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Permanent dipole, dipole
Present in polar molecules. Ex: H2O, NH3, HCl, CHCl3 Hydrogen bonding (H-bonding) H-bonding is present in molecules with possibility of H-bonding. This is by far the strongest type of intermolecular force. i.e. with: F-H, O-H, N-H bonds Hydrogen bonding is responsible for the liquid state of water, and water is responsible for the presence of life.

Ex: H2O, NH3, proteins, C2H5OH (carboxylic acids)

+ +
H O

H O

H +

+ H

Hydrogen bonding

Hydrogen bonding

END OF LESSON

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Chapter 4 (AS-Level)
States of Matter The three states:

Order

Disorder

Solid

Liquid
Kinetic Energy Winning

Gas

Intermolecular Forces Winning


Intermolecular forces tend to bring order to molecules, while kinetic energy brings disorder. Brownian motion occurs in only gases and liquids.

How much order is there in liquid?


There is short-range order and long-range disorder.
Arrangement of Particles in Solids

There are different types of solids: Giant Metallic (Metals) Giant Ionic (Ionic Compounds) Giant Covalent (Graphite, SiO2 diamond) Simple Covalent (I2)
Impurity

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Difference in properties of solids, liquids, and gases:
They are due to differences in spacing and speed of particles.
Spacing In gases, particles are much further apart than in liquids and solids. There is little difference between liquids and solids. Both (solids and liquids) are hard to compress Gases are poor conductors, because of the large distances between particles. Liquids and solids are better conductors For heat to be transferred by particles, movement of energy of particles must be passed from one to another (by collision in gases & liquids and vibration in solids). Metals are unique in thermal and electrical conduction due to the presence of free electrons. Solids Amount of order of arrangement of particles Shape Position of particles Spacing of particles Compressibility Conduction of heat Very orderly Liquids Short-range order; longer-range disorder Takes shape of the container Some movement Close (10-10 m) Very low Metals very good; others poor Gases Almost complete disorder No Shape Always moving rapidly Far apart (10-8 m) High Very poor

Fixed Fixed; no movement; vibration in place Close (10-10 m) Very low Metals & graphite conduct; others poor

Why gases liquefy and solids melt?


By bringing molecules closer (applying pressure) and slower (reducing their temperature), intermolecular forces become sizable and overcome repulsive forces. Molecules stick together leading to liquid state. Each gas has its characteristic T at which intermolecular forces are strong enough to win (T c critical temperature).

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For melting, heating is necessary, i.e. thermal energy to increase kinetic energy of molecules must be supplied to overcome intermolecular forces to allow molecules to be free to move.

Explaining changes of state

Fusion - Melting

Solid
Freezing - Solidification

Liquid

Evaporation - Boiling

Liquid

Condensation Liquefaction

Gas

Experiment to measure the vapor pressure of a liquid: Read page 57. Not required for examination.

At equilibrium, the rate at which molecules leave the liquid equals the rate at which molecules join the liquid.

A liquid boils when its vapor pressure equals atmospheric pressure.

Remarkable Substances:
Liquid Crystals
These are liquids which have sufficient long-range order to behave like solids (at certain range of temperature). Usually molecules are thin, long, and not very symmetrical. Arrangement of molecules can be upset by slight changes in the surroundings.

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Glass
It is in a state between solid and liquid, similar to a very viscous liquid which melts and remains viscous over a range of temperatures. The building block is tetrahedron of Silicon attached to 4 Oxygen atoms.

Real and Ideal Gases


Gases have the following properties: They fill the space available to them Expand when heated Exert pressure on the walls of the container Pressure Changes with temperature

Real Gases: are the gases that exist in reality, O2, N2, CO2, NH3, and etc.

Ideal Gases: Are theoretical gases which do not exist in reality. Mathematical model where: Molecules are regarded as points (do not occupy space) Molecules do not attract each other (no intermolecular forces) Their collisions are perfectly elastic

The Kinetic Theory of Gases


Gases consist of molecules (or atoms in noble gases) in a state of constant random motion. The pressure they exert is due to collisions with the walls of container. The molecules travel in straight lines between collusions with one another and with the walls of container. The total kinetic energy of the molecules does not change in collisions i.e. KE is conserved (elastic collisions)

Average Molecular Speed at the room temperature is of the order of 500 m/s. The speed is faster in lighter molecules (e.g. H2 1500 m/s). The speed is slower in heavier molecules (e.g. CO2 350 m/s). How the distribution of the kinetic energy of the molecules in a gas changes with temperature.

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The Pressure & Volume of Ideal Gas
Pressure is due to collisions on the walls of container due to continuous random motion. It depends on three factors. 1. The number of molecules per unit volume (i.e. concentration), the higher the number of particles higher the number of collisions the more pressure. 2. The mass of molecules 3. The speed of molecules The volume of a given amount of gas at a fixed pressure increases as temperature increases and decreases as temperature drops. The volume is directly proportional to temperature as in the graph .

The Ideal Gas Law


Note: You can replace n with m/Mr Ideal Gas Constant R=8.314 JK-1mol-1

Pressure in Pa Volume in m3 Number of moles, mol

Absolute Temperature. K (K=Celsius +273)

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Behavior of Real Gases
Real Molecules Real Molecules Occupy Space Attract each other Less volume than ideal volume Less pressure than ideal value

Real Gas Equation


Real gases approach ideal gas behavior quite away from conditions of their liquefaction. Opposite of Liquification= Low pressure (small intermolecular forces) and high temperature (large distances between molecules)

END OF LESSON

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Chapter 5a (AS-Level)
Chemical Energetics
Chemical reactions are accompanied by enthalpy changes, in the form of heat energy.

Enthalpy, given the symbol H, is the total energy content of thee reacting materials. Enthalpy change is the change in the total energy content of the reacting materials, given the symbol H (Delta H). When H is negative, the reaction is exothermic; when its positive the reaction is endothermic.

Some chemical reactions are: Exothermic: Examples: - Combustion of fuel - Respiration in our bodies - Reaction of metals with acids - Reaction of alkalis with acids - Reaction of quicklime with water:
CaO(s) + H2O(l)Ca(OH)2 (aq) + E

Endothermic: Examples: Decomposition of limestone: CaCO3(S) + E CaO(s) + CO2 (g) Photosynthesis: CO2 (g) + H2O + E Carbohydrates (Glucose) Dissolving NH4Cl: NH4Cl(s) + H2O + E NH4+ (aq) + Cl- (aq)

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Energy is conserved
Energy is neither created nor destroyed, in either exothermic or endothermic reactions. In endothermic reactions, the energy is transferred to the reactants (the system) from the surroundings. In exothermic reactions it is transferred to the surroundings, all in the form of heat.

Enthalpy and Enthalpy changes


Mentioned earlier are the definitions of enthalpy and enthalpy change.

H has a unit of kilojoules per mole (kJ mol-). We can illustrate enthalpy changes using Enthalpy Profiles (or Enthalpy graphs). Shown below are some examples:

Example:

( )

( )

( )

()

In which Delta H = -890 kJ/mol.

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Standard Enthalpy Changes (H)
When we want to compare the enthalpy changes of reactions, we must use standard conditions. A standard enthalpy change for a reaction takes place under these conditions, which are known as standard: Pressure = 1 atm = 100kPa Temperature = 298K Mole = 1mol Concentration = 1M =1 of solutions

Reactants and Products in normal physical and standard condition

Standard enthalpy change of reaction (Hr)


Hr is the enthalpy change when the amounts of reactants given in reaction equation react under standard conditions to give products in the standard conditions. Example: 2H2 (g) +2O2 (g) 2H2O(l) HR = -572kJ BUT H2 (g) + O2(g) H2O(l) HR = -286 kJ

Standard enthalpy change of formation of compounds (Hf)


HF is the enthalpy change when 1 mol of the compound is formed from its elements under standard conditions. Example: HF (H2O) = -286 kJ/mol

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Standard enthalpy change of combustion (Hc)
HC is the enthalpy change when 1 mol of the substance is completely burned in oxygen under standard conditions. Example: HC (H2) = -286 kJ/mol

Other enthalpy changes We can define other standard enthalpy changes in a similar manner: The standard enthalpy change of hydration is the enthalpy change when one mole of a gaseous ion dissolves in water to give an infinitely dilute solution. The standard enthalpy change of solution is the enthalpy change when one mole of a solute dissolves in a solvent to give an infinitely dilute solution. The standard enthalpy change of neutralization is the enthalpy change when one mole of H+ ions from an acid is completely neutralized by an alkali to give one mole of water. The standard enthalpy change of atomization of an element is the enthalpy change when one mole of gaseous atoms is formed from one mole of the element in its standard state.

Bond making, breaking and enthalpy change


Bond Making is Exothermic Bond Breaking is Endothermic

Bond Enthalpy (BE) is the energy needed to break 1 mole of a particular covalent bond. This indicates the strength of the bond, the higher the energy needed, the higher bond strength and vice versa.

Bond enthalpies It is useful to measure the amount of energy need to break a covalent bond, as it indicates the strength of the bond. It is called Bond Enthalpy. They are also:
All are positive quantities

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All are average values Compared from bonds in gaseous compounds Difficult to measure directly They are given in tables (such as data booklets which are given in AS/A level exams)

Example: Bond H-H C-C +347 C=C +612 C-H +413 O=O +498 O-H +464 C-O +358 C=O +805

Enthalpy +436 Change

Calculating Enthalpy change of a reaction from bond enthalpies:

CH4 (g) + 2O2 (g) Co2 (g) + 2H2O(l)


O=C=O Form 2 C=O bonds H H C H Break 4 C-H bonds Break 2 O=O bonds H H O=O O=O H O H O H

Form 3 O-H bonds

Hr = (sum of all BEs from broken bonds) (sum of all BEs from formed bonds)

Calculation:
HC = Hr = [4BE(C-H) + 2BE(O=O)] [2BE(C=O) +4BE(O-H)] = 4(413) +2(498) 2(805) 4(464) = -890kJ

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Measuring energy transfers and enthalpy changes
Enthalpy change of combustion Measurements of Hr are important as they help to compare the energy available from the
oxidation of different flammable liquids, which may be used as fuels. The apparatus is shown below:

Measurements that are taken: Mass of cold water The temperature rise of the water The loss in mass of the fuel The specific heat capacity of water is also needed, which is 4.2 Jg-1K-1. Specific heat capacity of a substance is the heat required to raise the temperature of a unit mass of a substance (one gram or one kilogram) one degree Celsius or Kelvin. Therefore:

While heat capacity of a substance or apparatus, is the heat required to raise the temperature of the whole substance or apparatus one degree Celsius or kelvin. Heat capacity is determined in a different experiment.

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Enthalpy change of combustion in
kJ/mol

Mass of liquid in calorimeter in grams


Heat Capacity of the liquid in Jg-1K-1


Change in temperature in K

See page 77 & 78 for diagram and explanation + solved example.

H of neutralization of acid and alkali

Use known amounts of acid and alkali (measured volumes and masses in case of solid Mix quickly and measure temperature change up to 0.1 degree Celsius to 0.2 degree accuracy Use the equation : Calculate for 1 mol of H+ Summary:
() () ()

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Enthalpy change of solution of NaOH Method: Use polystyrene cup to hold the solution. Weigh and add 100g distilled water. Determine initial temperature. Add few pellets of solid NaOH quickly to the water. Stir mixture immediately and start a timer to take temperature readings at regular intervals. Temperature rises to a max and then drops, readings should be taken for enough time. Weigh the cup and find mass of NaOH added. Plot temperature versus time and extrapolate to find T as in the figure.

Heat evolved = m x 4.18 x T Then calculate for 1 mole H solution Example: Mass of cup = 8g Mass of cup + water = 108.15g Mass of distilled water = 100.15g Mass of NaOH + cup + water = 114.35g Mass of NaOH = 6.20g Initial temperature of cup = 15 C From the graph, T = 16C

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Calculation: E = m.c.T E = 100.15 x 4.18 x 16 = 6700J released when dissolving 6.2g of NaOH. For 1 mole of NaOH 40 grams should be used (or calculated) to get the enthalpy change of solution of NaOH.

Enthalpy change by different routes (Hess law)


In chemical reactions:

Hess law states that: The total enthalpy change for a chemical reaction is independent of the route followed from reactants to the products, provided the initial and final conditions are the same.

So we deduce the following (using the diagram):

Hess law is another form of the law of conservation of energy, which is the first law in thermodynamics.

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Using Hess law in enthalpy change calculations A. Calculating Hr from bond enthalpy Example: In Habers process: N2 (g) + 3 H2 (g) 2 NH3 (g)

Hr = Hf = Broken bonds Formed bonds


Hr = Hf = BE (NN) +3 BE (H-H) 6 BE (N-H)

B. Calculating Hr from enthalpy changes of formation Hf Example (given the Hf of reactants and products): CaO (s) + H2O (l) Ca(OH)2 (s) O2 + Ca H2 + O2

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Hf (CaO) + Hf (H2O) + Hr = Hf [Ca(OH)2]

(Figures given by the examiner) (-6351) + (-285.8) + Hr = (-984.1) Hr = -65.2 kJ/mol of Ca(OH)2 Therefore: Hr = *Hf (Products)+ *Hf (Reactants)+ C. Calculating HFormation from HCombustion Example: Find Hf (CH4), given HCombustion C (s) 2 H2 (g) CH4 (g)

Hf (CH4) + HC (CH4) = HC (C) + 2 HC (H) Hf (CH4) = (-394) + 2(-286) (-890) Hf (CH4) = -76 kJ/mol

END OF LESSON

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Chapter 6 (AS-Level)
Electrochemistry
Elements have different combining power, which is different ratios of atoms that combine with each other is called valency (Strength). Example: MgO which has a ratio of 1:1 Al2O3 which has a ratio of 2:3

At present a more useful measure is used, Oxidation state or Oxidation number. The charge an atom would have in a molecule or ion, if electrons were completely transferred (to the more electronegative atoms) in covalent molecules or ions.

Rules for assigning oxidation numbers:


1. Oxidation numbers are calculated as the number of electrons that an atom loses, gains or shares in forming ionic or covalent bonds. 2. The oxidation state of free element is zero. E.g. H2, Br2, O2, etc. 3. The oxidation number of a simple ion (monatomic) is its charge. E.g. Na+ (+1) 4. The oxidation number of hydrogen in compounds is (+1), except in metal hydrides, where it is (-1) 5. The oxidation number of oxidation in compounds is (-2), except in peroxides and in OF2 where it is (-1) and (+2) respectively. 6. In the molecules and ions, the more electronegative atom in given the negative oxidation numbers. 7. The sum of oxidation numbers of all atoms in a neutral molecule is zero. 8. The sum of oxidation numbers of all atom in a complex ion is equal to the charge of the ion. Oxidation Numbers Calculation Examples: The oxidation number of Carbon in CO2 is: (-2) x 2 = (+4) The oxidation number of Carbon in CH4 is: X + 4 x(+1) = 0, therefore X = (-4) of Mn in KMnO4 is: 1 + X + 4(-2) = 0 X = +7 of Cl in KClO3 is: 1+ X + 3(-2) = 0 X = +5

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Redox Reactions:
Reduction Oxidation Reactions: The term redox is used for the simultaneous processes of reduction and oxidation, in which one element is reduced and another oxidized. Examples:

Both are redox reactions.

Fe is oxidized, it is the reducing agent. O is reduced it is the oxidizing agent.


From the example: Fe had an oxidation number of 0. After the reaction, the Fe lost 3 electrons, so its oxidation number increased. Similarly, the oxygen had an oxidation number of 0 before the reaction and gained 4 electrons, so its oxidation number decreased from 0 to -2.

Oxidation is: The loss of electrons. Increase in oxidation number. Reduction is: The gain of electrons. The decrease in oxidation number.

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Electrolysis
It is a redox Chemical reaction that takes place when a direct current is passed in an aqueous solution or molten ionic compound. Oxidation takes place at the anode. Reduction takes place at the cathode.

Example:
Electrolysis of H2O

4 OH- O2 + 2 H2O + 4 e4 H+ + 4 e- 2 H2
Net reaction: 4 OH- + 4 e- 2 H2O + 2 H2 + O2

More information available in the book.

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Electrolysis of Brine using Diaphragm cell

At the anode (oxidation): 2 Cl- 2 e- + Cl2 At the cathode (reduction): 2 H+ + 2 e- H2 Net reaction: H2O H+ + OHOH- + Na+ NaOH

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Extraction of Aluminium from Alumina

The method used to extract the metal form its ore depends on the position of the metal in the reactivity series. If the metal is high up in the series, its ores are stable and can be only be obtained by electrolysis. Aluminium is extracted from bauxite (Al2O3) by electrolysis. However, bauxite has a very high melting point but can be dissolved in molten cryolite at 900 degrees Celsius. In other words, the cryolite is used to lower the melting point of bauxite.

Cathode reaction: 4 Al3+ + 12 e- = 4 Al Anode reaction: 6 O2- = 3O2 + 12 eCarbon dioxide is also produced from this reaction. It is produced from the carbon electrodes burning in the heat and oxygen produced.

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Electrolytic purification of copper

Metals can be refined or purified by electrolysis. The impure metal forms the anode and the pure metal forms the cathode. The electrolyte is an aqueous metal salt. In the purification of copper, impure copper is used as the anode and a thin sheet of pure copper is used as the cathode. The following reaction occurs: At anode, the copper is ionized (becomes an ion): Cu -2e- = Cu2+ At the cathode, the copper ion is unionized, which produces solid copper on the cathode: Cu2+ +2e- = Cu As electrolysis takes place the pure copper sheet gains mass and the anode (impure copper) loses mass and the impurities are deposited under the anode in the container. This means that the copper ions had left the impure copper side and joined the pure copper side. The colour of the copper (II) sulphate solution does not change as the concentration of copper ions in the solution does not change.

END OF LESSON

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Chapter 7a (AS-Level)
Equlilibria
Reversible Changes:
1. Physical changes, examples: Melting of ice, freezing of H2O

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H2O H20 Dissolving CO2 in H2O like in fizzing drinks CO2 (aq) CO2 (g) 2. Chemical changes, examples: Formation of ozone and its decomposition to oxygen 3 O2 + UV Light + CFCs 2 O3 Thermal decomposition of CaCO3 to CaO and CO2, and the formation of CaCO3 from CaO left in an atmosphere of CO2 CaCO3 (s) CaO (s) + CO2 (g)

Equilibrium, a state of balanced change:


Examples: Dissolve salt in H2O until no more dissolves (saturated solution + non-dissolved salt) = equilibrium between solution and solid, which is concentration of saturated solution stays constant (at a constant temperature). Although the ions are in constant motion, moving from solid to solution and to solution to solid. NaCl (s) Similar equilibrium in butane cylinder. Molecules in liquid are in equilibrium with those in the gas phase C4H10 (l) C2H10 (g) Na+ Cl- (aq)

Equilibrium and chemical changes


For example: CaCO3 + Heat CaO + CO3 There is no equilibrium in an open container. CaO + CO2 CaCO3

In an atmosphere of carbon dioxide in a closed container.

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Both reactions occur when put in a closed container at a high temperature. Balance is reached between reactants and products All chemical reactions can reach equilibrium where reactants are in equilibrium with the products (Dynamic equilibrium) In some reactions, the degree of conversion of reactants into products is so large, e.g. burning Magnesium in air. In others, e.g. nitrogen and oxygen, seem not to react at all Equilibrium is highly in favor of products or reactants. So some are almost irreversible

Characteristic features of equilibrium


It is dynamic at molecular and ionic levels Both forward and backward reactions take place at equal rate A closed system is required Macroscopic properties remain constant

Le Chateliers principle
When any condition affecting equilibrium is changed, the position of the equilibrium will shift in the direction to minimize that change
Effect of temperature on the position of the equilibrium

For example: CaO + CO2 CaCO3

The higher the temperature, the more decomposition happens, so the equilibrium position shifts to the left.
If the forward reaction is exothermic, raising the temperature moves the equilibrium to the right and vice versa. Effect of changing the concentration on equilibrium position

For example: We will consider the formation of the ester, ethyl ethanoate. When Ethanoic acid is warmed with ethanol, in the presence of a few drops of concentrated sulphuric acid, ethyl ethanoate is formed. CH3COOH + CH3H2OH CH3COOCH2CH3 + H2O

The sulphuric acid is a catalyst for this reaction. Equilibrium is formed as soon as the reactants are mixed. If we increase the concentration of one of the reactants, the equilibrium moves to the right to increase the concentration of the products, to decrease the concentration of the reactants.
Increasing the concentration of a reactant makes the equilibrium move in the direction that decreases the concentration of the reactant. Effect of pressure on equilibrium position

If we increase the pressure of a gas, its concentration would also increase. For example: 3 H2 + H2 2 NH3

Increasing the pressure moves the equilibrium to the right, producing fewer molecules.

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In general, increasing the pressure shifts the equilibrium to the side of fewer gaseous molecules and vice versa. Effect of catalyst on equilibrium Catalysts have no effect on equilibrium, but allow the equilibrium to be achieved faster.

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They do this by decreasing the activation energy, and hence speed it up. More catalyst could mean a faster reaction rate, but doesnt change the equilibrium concentration of reactants or products.

Law of chemical equilibrium


For the general equation: aA +bB The following is always true: cC + dD

KC is the equilibrium constant; A, B, C and D are the concentration of the corresponding substances in the general equation; The superscript, a, b, c and d are moles of the corresponding substances in the general equation. For example: H2 + I2 2HI

Calculating KC

For example: OH CH3COCH3 + HCN CH3CCH3 CN Initial concentration Change 0.05 mol/dm3 -0.0233 mol/dm3 0.05 mol/dm3 -0.0233 mol/dm3 0.00 mol/dm3 +0.0233 mol/dm3

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KC and Le Chateliers principle

For example: 2 HI When the temperature is raised: The concentration of products increase, while the concentration of reactants decrease, so KC has to increase. Example 2: 2 SO2 + O2 2 SO2 Forward reaction is exothermic H2 + I2 Forward reaction is endothermic

The concentration of the product decrease as the temperature is increased, while the concentration of the reactants increases, so KC has to decrease.
KC and concentration changes

For example: 2 HI At 500K, H2 + I2

If the concentration of HI is increased, KC decreases. So to maintain equilibrium, the concentration of H2 and I2 has to increase so the value of KC reaches 6.25x10-3.

Equilibrium constants and pressure changes


In reactions involving gases, KP (of pressures) is used. E.g. 2 HI ( H2 + I2 ) ( ) ( )

p(H2) indicates the equilibrium partial pressures of H2 in a closed system containing the equilibrium mixture at constant temperature. The partial pressure of a gas in a mix of gases is the pressure exerted by that gas alone, if it occupies the container alone.
Calculating partial pressures

For example, air at 500kPa has 1 mole oxygen and 4 moles nitrogen. (1) Mole fraction = Of oxygen = , and of nitrogen = (2) Partial pressure = mole fraction x total pressure

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p(O2) = x 500 = 100kPa p(N2) = x 500 = 400kPa

Haber process and KP


The Haber process is a process in which ammonia is produced from reacting hydrogen and nitrogen together. The reaction is: N2 (g) + 3 H2 (g) 2 NH3 (g)

The conditions are: A pressure between 2.5 and 15 MPa A temperature between 670K to 770K In terms of partial pressures of nitrogen, hydrogen and ammonia, the equilibrium constant expression is: ( ( ) ) ( )

Using KC and KP
Example 1: CH3COOH(l) + C2H5OH(l) KC = Example 2: H2(g) + I2 (g) 2HI(g) CH3COOC2H5 (l) + H2O(l)

KC =
Example 3: 3H2(g) + N2(g) KC = Example 4: Mixture of 0.500 mol/dm3 H2 and 0.500 mol/dm3 I2 was placed in a 1.00 dm3 stainless-steel flask at 430 degree Celsius. Calculate the equilibrium concentration of H2, I2 and HI. KC of the reaction is 54.3 at this temperature. 2 HI H2 + I2 2NH3(g)

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Initial Change Equilibrium 0.500 mol/dm -X mol/dm3 (0.500 x) mol/dm3
3

0.500 mol/dm -X mol/dm3

0.00 mol/dm3 2x mol/dm3 2x mol/dm3

(0.500 x) mol/dm3

( ( ( ( ( ( ( ) ) ) ) ) )(

) ) ( ( )( )( ( ) ) ) ) )

( (

So the equilibrium concentrations are: Equilibrium 0.091 mol/dm3 0.091 mol/dm3 0.818 mol/dm3

The Haber process


3 H2(g) + N2(g) 2NH3(g) (H = -93 kJ/mol) Due to the unreactive nature of nitrogen, a high amount of energy is needed. Increasing the temperature would drive the equilibrium to the left as the forward reaction is exothermic. Pressure is also used to increase the reaction rate, which would drive the equilibrium to the right. Very high pressures increase the cost of the plant, and low pressures make the reaction very slow. A catalyst can be used to overcome the problem of the low rate of reaction. An iron catalyst is used, with small amounts of K, Mg, Al, and Si oxides that improve the efficiency of the catalyst. The rate of the reaction can be increased by increasing the temperature and by accepting a lower equilibrium percentage of ammonia in the mixture. Ammonia is removed as it is formed, so the reaction mixture is not left to reach equilibrium. Rapid expansion is used to cool the mixture. Ammonia liquefies, while unreacted nitrogen and hydrogen are recycled into the reaction vessel. Conditions are: Between 2.5 and 15MPa pressure 670 to 770K temperature Finely divided or porous iron catalyst with metal oxide promoters

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The contact process


In this process, sulphuric acid is manufactured from sulphur. (1) Sulphur is burned in air at 1000C to make SO2 S + O2 SO2 (2) Sulphur dioxide is converted into Sulphur trioxide by using vanadium (v) oxide catalyst. 2 SO3 + O2 2 SO3 (H = -197 kJ/mol) (3) Sulphur trioxide is dissolved in sulphuric acid to make oleum (H2S2O7) which is then diluted into sulphuric acid. SO3 + H2SO4 H2S2O7 H2S2O7 + H2O 2 H2SO4 Conditions are: V2O5 catalyst Temperature of 400 to 600C Pressure just above atmospheric pressure These conditions used to convert sulphur dioxide into sulphur trioxide are a compromise. Higher yields of SO3 are produced when using air in excess, forcing equilibrium to the right. A temperature of 400C is used because the catalyst is inactivated below it. Uses of sulphuric acid include: The manufacture of paints The manufacture of detergents and soaps The manufacture of phosphate fertilizers The manufacture of dyestuff

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Acids and their reactions


General properties of acids: E.g.: Turn blue litmus red Have a pH below 7 Produce CO2 when they react with carbonates Neutralized by alkalis and bases

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HCl (g) + H2O (l) H3O+ (oxonium ion) (aq) + Cl-

Salt formation by acids


Reaction of hydrogen chloride and ammonia:

HCl

White solid NH4Cl HCl + NH3 NH4Cl

NH3

Or HCl + NH3 NH4+ + Cl-

Production of fertilizers

2 NH3 + H2SO4 2 NH4+ (aq) + SO42- (aq)

H2SO4 donated a proton to ammonia to make the NH4+ ions. 2 NH3 + 2 H+ (aq) + SO42- (aq) 2 NH4+ (aq) + SO42- (aq) Simplified into: NH3 NH4+ + H+

Formation of salts with metals, metal oxides and metal carbonates


With metals

2 H+ + 2 Cl- + Mg Mg2+ + 2 Cl- + H2 Cancelling out spectator ions: 2 H+ + Mg Mg2+ + H2


With metal oxides

2 H+ + 2 Cl- + CuO Cu2+ + 2 Cl- + H2O Cancelling out spectator ions: 2 H+ + CuO Cu2+ + H2O

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With metal carbonates

2 H+ + 2 Cl- + CuCO3 Cu2+ + 2 Cl + H2O + CO2 Net ionic equation: 2 H+ + CuCO3 Cu2+ + H2O + CO2

Definition of acids and bases


Arrhenius (1884):

An acid is a substance that produces an excess of H+ in aqueous solutions A base is a substance that produces excess of OH+ in aqueous solutions.
Brnsted & Lowry

An acid is proton donor. A base is a proton acceptor. Examples: When hydrochloric acid dissolves in water:
HCl + H2O H3O+ + Cl-

Proton Donor

Proton Acceptor

Conjugate acid of H2O

Conjugate base of HCl

When ammonia dissolves in water:

Ammonia accepts a proton from the water and so its a base. The ammonium ion is its conjugate acid. Water donates a proton, so its an acid. The hydroxide ion is its conjugate base.

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The role of water

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Pure water conducts electricity. This is a fact. This means that pure water contain ions of itself. Pure water can also be electrolyzed by a direct current. Every now and then, one water molecule reacts with another water molecule to form ions. A proton leaves one water molecule and is accepted by the other. These ions transfer electrons during electrolysis. 2 H2O (l) Or more simply as: H2O (l) H+ (aq) + OH- (aq) H3O+ (aq) + OH- (aq)

Base behavior and neutralization


When acid and bases react, they are said to neutralize each other. For example, in the acid HCl, there are 2 ions, H+ and Cl- and a water molecule. In the base NaOH, there are Na+ and OH- ions and a water molecule. When these are mixed, the protons and hydroxide ions react to form water. H+ (aq) + OH- (aq) H2O (l) (H= -57 kJ/mol)

This is what neutralization is the formation of water by the exothermic forward reaction. The ions remaining stay dissolved in water.

Acids and bases of varying strength


Strong acid and bases are those which are totally ionized when dissolved in water. The strong acids include hydrogen halides and strong bases include the group I hydroxides. Weak acids and bases dont ionize totally when they dissolve in water. They even might not ionize at all. Examples for weak acids include Ethanoic acid. They hardly donate protons at all.Organic acids like Ethanoic acid and citric acids are typical weak acids. Weak acids are similarly weak in accepting protons. These include the conjugate bases of strong acids, such as sulphate and chloride ions. Acid Strongest acid Hydrochloric Benzoic Ethanoic Ammonium Phenol Weakest acid
Hydrogen carbonate
HCl H + Cl
+ -

Base Chloride Benzoate Ethanoate Ammonia


-

Weakest base

C6H5COOH H + C6H5COO CH3COOH H + CH3COO NH4


+ +

H + NH3
+

C6H5OH H + C6H5CO HCO3


-

Phenoxide Carbonate hydroxide Strongest base

H + CO3
+ -

2-

Water
END OF LESSON

H2O H + OH

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Chapter 8a (AS-Level)
Reaction kinetics Rates of reaction why bother?

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There are many reasons why chemists study the rate of reaction, for example to: Gain insight into the reaction mechanism (how the reaction proceeds). Understand the chemical processes taking place in our bodies and environment. Improve the rate of the production in chemical industries.
When a reaction proceeds through several steps, the slowest step in the mechanism determines the overall rate of the reaction, and it is called the rate-determining steps.

Chemical reactions proceed at different rates


The rate of reactions tells us how fast the reaction occurs. It is measured by amount of a reactant used up, or the amount of product produced, in a given time.

OR:

The reaction rate is a positive quantity. Example: H2O2 + 2 I +2 H 2 H2O + I2 If concentration of I2 is changed from 0 to 10-5 mole in 10 seconds, then the reaction rate is:

The unit is always mol.dm-3.s-1 When t approaches 0, , which is the instantaneous reaction rate at time t. In practice, it is the slope of the tangent at time t, to the concentration-time curve.

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Rate at time t1 > rate at time t2


Reaction rate starts high and then decreases with time.

Factors affecting the reaction rate


1. Concentration of reactants In general, increasing the concentration of the reactants increases the reaction rate. Example: 2 HCl + Mg MgCl2 + H2 Increasing HCl increases the rate, which is seen as more vigorous evolution of H2. In gaseous reactions, increasing the pressure increases the reaction rate e.g. as in Habers process. 2. Temperature In general, increasing the temperature increases the rate. Increasing the temperature by 10 degrees, increases the rate by a factor of 2 (doubles the rate). For example, a catalytic converter only functions properly if it is hot, as the reactions on the surface of the catalyst are negligible when it is cold. 3. The surface area in heterogeneous reactions Increasing the surface area of a solid or liquid reactant increases the rate. Example: 2 HCl + Mg MgCl2 + H2 Magnesium may be in ribbon or powder form. Using the powder form, the reaction is a lot faster.

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4. In some reactions, the intensity of light Increasing the light intensity of radiation (visible or UV light) increases the rate. For example, in the free radical substation of methane by chlorine, an increase in the intensity of UV light increases the rate of the reaction. 5. Catalysts Catalysts usually speed up the reaction by lowering the activation of the energy of the reaction. For example, nickel is used in the hydrogenation of vegetable oils to make margarine.

Monitoring and measuring reaction rates


We can measure reaction rates in a variety of ways to study the factors which affect the chemical reaction rates. To study the effect of temperature on a reactions rate, all the other variables must be kept constant, while the temperature may be changed. A fair test is required. We must also know the mole ratios of the reactants and products as shown by the balanced chemical equation. No side reactions must be taking place, as these will affect the measurements. Now the way in which the reaction progress can be monitored must be decided. There are 2 types of method accessible to us: 1. Destructive method This based on chemical analysis, for example, using titration. Samples are taken from reaction mixture at suitable intervals, quenched (to stop the reaction, using ice for example) and analyzed (and the concentration is determined). 2. Non-destructive methods This is done using physical methods to measure a property that changes as reaction proceeds. Properties like mass, volume, pressure, pH, colour, electric conductivity can be used at regular time intervals (quenching not included).
Monitoring reaction rate using mass loss

When a gas is evolved during a reaction, monitoring mass loss may provide a suitable method of measuring the reaction rate. There needs to be sufficient loss in mass to be followed using a reasonably accurate balance. For example, 2.00 g of small marble chips will give a satisfactory loss in mass when treated with 150 cm3 of hydrochloric acid.

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Ideally, the mass loss can be monitored using a computer. The following figure shows the apparatus used to measure the mass loss during the reaction of marble chips with hydrochloric acid. The following figure shows the computer-generated graph showing mass loss against time. The gradient shows the reaction rate at time t.

Monitoring the reaction rate using volume of gas evolved

The reaction of calcium carbonate with hydrochloric acid may also be monitored by collecting the carbon dioxide evolved. The gas may be collected in a gas syringe or in an inverted water-filled burette. The volume of carbon dioxide produced over a period of time is proportional to the reaction rate. The following figure show the apparatus used to measure the reaction rate.

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Monitoring reaction rate using colour intensity

Using colour intensity, concentration of a specific substance can be measured. For example, the concentration of copper ions in the following experiment can be estimated using a spectrophotometer.

The copper ions replace the atoms of iron. After several minutes, the blue colour of (a) has become paler and a red-brown deposit has formed on the iron wool (b). The spectrophotometer is a device that measures how much light of a particular wave-length can pass through a sample, liquid or gas. The beaker in (a) contains 1 dm3 of 1.00 mol dm-3 aqueous copper sulphate. Iron wool reacts with the copper ions in the solution, displacing them and changing the colour of the solution as a result. Cu2+ (aq) + Fe (s) Fe2+ (aq) + Cu (s) Solutions appear coloured because they absorb radiation in the visible region of the spectrum. Aqueous copper sulphate absorbs radiation in the yellow, orange and red regions, which only allows blue light to pass through and so the solution looks blue.
Measuring reaction rates of gases using pressure changes

Measurements of pressure changes at a given temperature can be used to calculate concentration change as a reaction proceeds. For example, this method can be used to monitor the production of carbon dioxide from limestone in a sealed container. CaCO3 (s) CaO (s) + CO2

The figure shows a notional system to investigate the effect of heat on the decomposition of limestone.

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Monitoring reaction rates of solutions using chemical analysis

If there is a change in acidity or basicity as a reaction proceeds, suitable titrations can be made to follow the rate. The rate of formation of sulphurous acid, H2SO3 (a component of acid rain formed by the reaction of SO2 with water), could be followed by measuring the increase in concentration of hydrogen ions produced. This is monitored by titrating samples of the increasingly acidic solution against a basic solution of known concentration, for example, 0.001 mol dm-3 aqueous sodium hydroxide. The more sodium hydroxide that is needed to neutralize the sample, the more sulphuric acid is present.

The collision theory of reactivity


For a reaction to occur: 1. There should be collisions between the molecules of reactants 2. These collisions should be energetic enough 3. They should occur with the right orientation of molecules Important points: Molecules will react only if they collide with each other And if there is enough energy in the collision Increasing the concentration increases the probability of collision of collision, which increases the rate of the reaction Increasing the temperature increases the proportion of molecules with sufficient energy to react, which increases the rate of reaction

The Boltzmann distribution of molecular energies


The Boltzmann distribution represents the number of particles with particular energies.

Billions and billions of particles in a gas are in constant random motion. A few are almost motionless. A minority have momentarily speeds far above the average. The majority of particles have speeds around the average. This is shown by the graph below. The difference between the energy of the molecules is only due to speed (as they have the same mass).

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When the sample is heated, the mean energy of the molecules increases. There is a wider spread of values.

Activation energy is the minimum energy needed in a collision in a given reaction to be productive. It is shown on the above graph and the one before it as the line before the shaded area. It is shown by Ea and has a unit of kJ mol-1. For example, in the oxyacetylene torch, the molecules of oxygen and ethyne will not react together even if they collide, as the outer shell electrons of both molecules repel each other. This repulsion can only be overcome by a substantial input of energy that bonds would be broken and attractive forces can take over. This boost of energy is given by igniting the mixture of the gases. This is shown diagrammatically in the following graph.

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With a catalyst:

A catalyst is a substance added to reactions in the purpose of increasing the rate. It doesnt change at the end of the reaction. It lowers the energy of activation which is achieved by allowing the reaction to take place by a different mechanism or by a different pathway. The reaction rate increases because the catalysed reaction pathway has lower activation energy than that of the uncatalysed reaction. The Boltzmann distribution below shows how the lower activation energy increases the number of molecules that will react on collision.

Enzymes
These are proteins that act as biological catalysts. Enzymes: Show great specificity Are extremely sensitive to changes in pH and temperature Are extremely sensitive to molecules that are inhibitors and cofactors Are far more efficient than the inorganic catalysts used in the chemical industry

END OF LESSON

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Chapter 9 (AS-Level)
Chemical Periodicity Versions of the periodic table

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The most common versions of the periodic table include vertical groups I, II, VII, and horizontal periods from 1 to 7 and blocks of elements, and are named as follows: S-block, which contains groups I &II P-block, which contains groups III to VII & 0 D-block, which contains transition metals F-block, which contains lanthanides & actinides

Periodic patterns of physical properties of elements (the first 36 elements only)


Electronic configuration:
In S-block, the outermost electrons are in s-orbital, in p-block the outermost electrons are in the p-orbitals. Elements in same group have the same number of electrons in their outer shell For the elements in groups I 0 the number of outer shell electrons is the same as the group numbers Group 8 (noble gases) have 8 es in their outermost shell.

Atomic radii
Atomic radius is 2 types: Covalent radius, which is half the distance between nuclei in neighboring atoms in a molecule. Metallic radius, which is half the distance between neighbouring nuclei in metallic crystal (lattice). Trends in atomic radii: Increase down a group Decrease across a period Relatively constant in T.M energies Opposite trends to ionization energies

These trends are due to the combined effect of: Nuclear charge Distance of outer electronic shell from nucleus (atomic size) Shielding effects of inner electronic shells

Ionic radii
Ionic radii decrease across a period The radii of positive ions (cations) are smaller than those of corresponding atoms

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The radii of anions are bigger than those of corresponding atoms

Melting points
Melting points increase across a period and reach peaks for elements in group IV. Carbon, Silicon etc. have high melting points which is due to strong covalent bonds forming a giant molecular lattice. Then a sharp decrease in melting point to form troughs for elements which form simple molecules or single atoms, H2, N2, O2, F2, He, Ne, Low melting points are due to weak inter-molecular forces. In groups I, II, II, melting points increase due to metallic bond is much stronger.

Electrical conductivity

Unit of electrical conductivity is siemens/meter (Sm-1) which is -1m-1. Electrical conductivities are much higher for metals than nonmetals and metalloids.
H:Li: 0.108 Be: 0.25 B: 10-12 Al: 0.382 C: 7 x 10-4 Si:2 x 10-10 P: 1017

He N O F Ne

Na: 0.218

Mg: 0.224

S: 1023

Cl

Ar

K: 0.143

Ca: 0.218

Sc: 0.015

Ti: 0.024

V: 0.04

Cr: 0.078

Mn: 0.054

Fe: 0.010

Co: 0.16

Ni: 0.145

Cu: 0.593

Zn: 0.167

Ga: 0.058

Ge: 2.2 x 10-8

As: 0.0 29

Se: 0.08

Br: 10
-18

Kr

First Ionization energies (IE)

Peaks are occupied by group 0 (Noble gases) Troughs are occupied by group I There is a general increase in IE across a period from group I to group 0, but the trend is uneven The variation in IE in transition metals is relatively small For example, considering F, Ne and Na:

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F: 1s , 2s , 2p 1680 kJ/mol Ne: 1s2, 2s2, 2p6 2080 kJ/mol Na: 1s2, 2s2, 2p6, 3s1 494 kJ/mol This is due to the combined effect of these factors: Nuclear charge (protons in nucleus) Atomic size (distance of outer electrons from nucleus) Shielding effect of inner shells
First ionization energies in periods

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Considering Li, Be and B: Li: 1s2, 2s1 IE = 519 kJ/mol Be: 1s2, 2s2 IE= 900 kJ/mol (Has the same shielding effect but greater nuclear charge and smaller size). B: 1s2, 2s2, 2p1 IE = 799 kJ/mol (The electron in the p-orbital is of higher energy level, so is easier to remove). From the above graph, a general trend can be seen across periods, but this trend is uneven. For example look the above elements, Lithium, Beryllium and Boron. Someone might predict that Boron has the highest first ionization energy, but Beryllium does. From experimental evidence like this, it is known that it is easier to remove electrons from a p orbital than from a s orbital in the same shell. P orbitals are higher energy levels than the s orbitals for a given quantum number. So an electron is easier to remove from the p orbital of the Boron atom than from the s orbital.
First ionization energies in Groups

Elements are placed in groups in the periodic table, as they show similar physical and chemical properties. The first ionization energies decrease down a group. This is due to: Nuclear charge increasing Atomic radii increases, so there is less attraction between electrons and protons Shielding effect of inner electrons The last two factors decrease the effect of the first factor.
First ionization energies and reactivity

The lower the first ionization energy of an element in the periodic table, the higher the reactivity of that particular element with acids or bases, with metals or non-metals. In reactions between metals and non-metals, the metal has to form a positive ion for a reaction to occur. The metals with lower first ionization energies react faster and more vigorously. Group I metals have the least first ionization energies because they have the lowest first ionization energies. Reactivity increases down the group.

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Reactions of period 3 elements

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MgO has a very high melting point and withstands corrosive chemicals. It is also used as an additive to cattle feed. Without it cattle become ill very fast. Al2O3 layer forms over aluminium metal, which prevents it from further reacting. SO2 used to produce H2SO4 which is used in the manufacture of paints, dyestuff, etc. NaCl is used a table salt, to remove snow from roads, etc. MgCl2 is used as a source for Mg and Cl2 CCl4 is used as a grease dissolver. SiCl4 is used as a source of pure silicon for the manufacture of Integrated circuits.

Preparation of period 3 oxides


Na2O: Sodium is burned in oxygen, which makes sodium oxide. It burns with a yellow flame. 4 Na + O2 2 Na2O MgO Magnesium is burned in air. It burns vigorously with a white flame. 2 Mg + O2 2 MgO Al2O3 Aluminium forms Al2O3 when powdered and burned. It is also a layer over the metal. 4 Al + 3 O2 2 Al2O3 P4O10 Phosphorous is burned in oxygen (excess). P4 + 5 O2 P4O10 SO2 and SO3 Sulphur is burned in air. S + O2 SO2 SO2 can be turned into SO3 by using V2O5 as a catalyst with heat an air. 2 SO2 + O2 2 SO3

Preparation of period 3 chlorides


NaCl Sodium burns in chlorine gas to make NaCl. 2 Na + Cl2 2 NaCl MgCl2 Magnesium burns in chlorine gas to make MgCl2.

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Mg + Cl2 MgCl2 AlCl3 Aluminium is heated in chlorine gas. A white volatile solid is formed. 2 Al + 2 Cl2 2 AlCl3 SiCl4 Silicon is heated in chlorine gas. SiCl4 is a volatile liquid. Si + 2 Cl2 SiCl4 Phosphorous (III) and Phosphorous (V) chloride PCl3 is a volatile liquid (colourless). P4 + 6 Cl2 4 PCl3 PCl5 is made when there is an excess of chlorine gas. P4Cl3 + Cl2 PCl5

The reactions of sodium and magnesium with water


Sodium Sodium is put in water. It floats and fizzes about. Sometimes it may catch fire. 2 Na + 2 H2O Mg(OH)2 + H2 NaOH has a pH of 12 -14 because it is very soluble and has a high concentration of OH- ions. Magnesium Magnesium is put in cold water. Hydrogen bubbles are formed slowly and a solution of Mg(OH)2 is formed. Mg + 2 H2O Mg(OH)2 + H2 If Magnesium is put in steam, MgO is formed instead. Mg + H2O MgO + H2 Important: Sodium is more reactive than magnesium, so sodium hydroxide is more alkaline than Mg(OH) 2 because it is more soluble.

Structure and bonding of oxides and their reactions with water


Na2O giant ionic lattice structure Na2O + H2O 2 NaOH (aq) pH 12-14 MgO giant ionic lattice structure

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MgO + H2O Mg(OH)2 (aq) pH 9-11 Al2O3 giant ionic lattice structure with a significant amount of covalent bonding. Insoluble in water. P4O10 covalent bonding; reacts vigorously with water to make phosphoric acid pH 2-4. P4O10 + 6 H2O 4 H3PO4 SO2 simple molecular structure with no intermolecular forces. SO2 + H2O H2SO3 SO3 simple molecular structures with Van der Waals forces SO3 + H2O H2SO4

Structure and bonding of chlorides and their reactions with water


NaCl and MgCl2 giant ionic lattice structures with ionic bonding NaCl + H2O NaCl (aq) MgCl2 + H20 MgCl2 (aq) Al2Cl6 is a diametric covalent molecule with 2 co-ordinate bonds. The arrangement around each aluminium atom is tetrahedral. Al2Cl6 + 12 H2O 2 [Al (H2O)6]3+ (aq) + 6 Cl- (aq) Silicon (IV) chloride and phosphorous (III) chloride have simple molecular structures with covalent bonding. PCl5 is a covalent molecule as a gas. Both react with water vigorously in an exothermic reaction giving off white fumes of HCl gas. This process is called hydrolysis. Hydrolysis of silicon (IV) chloride: SiCl4 (l) + 2 H2O SiO2 + 4 HCl Hydrolysis of phosphorous (V) chloride: PCl5 + 4 H2O H3PO4 (aq) + 5 HCl (g)

END OF LESSON

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Chapter 10a (AS-Level)


Group II General properties of group II elements:

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They are all metals They are good conductors of electricity Their compounds are all white or colourless They all have an oxidation number of +2 in their compounds They are called the alkaline earth metals because their oxides and hydroxides are basic They react with acids to give hydrogen gas

Compared with group I elements: They are harder and denser Have a higher melting point Exhibit stronger metallic bonding due to 2 outer shell electrons

Uses
Magnesium
It is used in flares, incendiary bombs and tracer bullets It has a strong reducing power, so is used to protect metals from corrosion. It is also used to extract less electropositive metals like titanium in the Kroll process at 1250K under an argon atmosphere. 2 Mg + TiCl4 Ti + 2 MgCl2 It is found in chlorophyll Mg(OH)2 is a weak alkali used in indigestion medicines and toothpastes. Mg(OH)2 + 2 H+ Mg2+ + 2 H2O MgO is a refractory material (resistant to heat, melting point over 3000K). It is used as a lining for furnaces MgF2 is used to coat the surfaces of camera lenses, to reduce the amount of reflected light (responsible for the violet colour of lens surfaces)

Calcium
CaCO3 (limestone) is used to make cement CaO (quicklime) is used to purify iron CaO + SiO2 CaSiO3 CaO glows with a bright light when heated Ca(OH)2 (solid) is used to reduce the acidity of soils Ca(OH)2 + 2 H+ Ca2+ + 2 H2O Plaster of Paris (calcium sulphate 2CaSO4.H2O) when mixed with water hydrates to CaCO4.2H2O and sets hard. It is used to set broken bones and for modeling The hydrogen carbonate of Ca and Mg are responsible for the hardness of water

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Barium

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Barium sulphate is used in the Barium metal, which is insoluble and coats the lining of the alimentary canal to make any imperfections visible for x-ray photographs. It is insoluble so is used as a test for the sulphate ions as it forms a precipitate.

Strontium
Strontium has a few uses. 90Sr is a product of many nuclear reactions.

Reactions of group II elements


With water
All group II elements produce H2 with water reducing it to H2. Mg reacts slowly with water to produce an alkaline solution of Mg(OH)2 and H2 Mg + 2 H2O Mg(OH)2 + H2 Mg reacts with steam to produce MgO, which is a rapid reaction. Mg + H2O MgO + H2 The reactivity of the elements with water increase down the group. Ca to Ba reacts readily with water to form a cloudy white precipitate of the hydroxide.

With oxygen
The reactions are vigorous once started. 2 Mg + O2 2 MgO

Formation of salts with HCl


All salts of group II elements are crystalline and white. They are prepared by the reaction of the metal, oxide or carbonate with an acid. Mg(s) + 2 HCl(l) MgCl2 + H2 (rapid with cold HCl) MgO(s) + 2HCl(aq) MgCl2(aq) + H2O(l) (rapid with heating) MgCO3 + 2 HCl(aq) MgCl2 + H2O + CO2 (rapid with cold HCl)

Reactions of oxides with water


All are basic and form a solution of the hydroxide (alkaline) MgO + H2O Mg(OH)2 (aq) BaO + H2O Ba(OH)2 (aq) The reaction of MgO with water is slow, others react readily with water The solubility of the hydroxides increase down the group and become more alkaline

Thermal decomposition of Group II nitrates and carbonates


All nitrates decompose to form metal oxides, nitrogen dioxide and oxygen: 2 Mg(NO3)2 2 MgO + 4 NO2 + O2 All carbonates decompose to form metal oxide and carbon dioxide: BaCO3 BaO + CO2 Decomposition temperature increase down the group

Chalk and lime industry


Chalk and limestone are both Calcium Carbonate Heating CaCO3 produces CaO (quicklime) and CO2

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CaCO3 CaO + CO2 CaO reacts with H2O to make Ca(OH)2 (slaked lime) CaO + H2O Ca(OH)2 Adding more water to calcium hydroxide produces lime water (pH 9 -10) Adding more CO2 to Ca(OH)2 (aq) form a cloudy precipitate of CaCO3 Ca(OH)2 (aq) + CO2 CaCO3 + H2O Adding more CO2 to the lime water after the precipitate, the mixture becomes clear again. The CaCO3 reacts with the water and CO2 (aq) to make Calcium hydrogen carbonate Ca(HCO3)2 CaCO3 + H2O + CO2 (aq) Ca(HCO3)2 Hard water contains Mg2+ and Ca2+ ions which react with soap to produce scum. These ions are come from the action of H2O and CO2 with CaCO3. The CO2 (aq) is formed when rainwater dissolves CO2 in the air. Flue gas desulphurization (FGD) CaCO3 is used to remove SO2 from waste gases produced when coal is burned. These gases are passed through a suspension of CaCO3 forming CaSO4 CaCO3 + SO2 CaSO3 + CO2 2 CaSO3 + O2 2 CaSO4 The CaSO4 is used to make plaster.

END OF LESSON

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Chapter 12 (AS-Level)
Group VII
These are called the halogens. They are non-metals.

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General properties of group VII elements


They behave in a similar chemical manner Non-metals Exist as diatomic molecules Melting and boiling points increase down the group Colour deepens down the group Very reactive and readily form salts Can exist in covalent and ionic compounds Reactivity decreases down the group They exhibit a range of oxidation numbers Electronegativity decrease down the group Their oxidation power decrease as going down the group

The reactivity of halogens


Displacement reactions
The electron affinity (enthalpy change for X + e- X-) is the ease at which a halogen can become an ion. The more negative the greater this ease and the greater the power of the oxidizing of the halogen The oxidizing power of the halogens decrease down the group as their reaction affinity increases (nearer to positive) Displacement reactions can occur as the oxidizing power of the halogens decrease down the group and any halogen can displace any other halogen lower in the group Cl2 + 2 Br- (aq) 2 Cl- (aq) + Br2 (aq) Cyclohexane is used, which forms a separate layer in which the ions are more soluble in it, so the colour becomes more apparent. Halogen Cl2 Br2 I2 ClNo reaction No reaction BrOrange-yellow No reaction IPurple iodine Purple iodine -

Reactions of halides with H2


H2 + X2 2 HX H2 + Cl2 2 HCl (explosive in UV light) H2 + Br2 2 HBr (reaction slow on heating) H2 + I2 2 HI (incomplete reaction on heating)

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All hydrogen halides formed are simple molecular compounds which are gases at room temperature The H-X bond length increases down the group, so the bond enthalpy decreases The bond enthalpy decreases down the group. This means that the stability of the hydrogen halides also decrease down the group HCl is stable at 1500C HBr decomposes at 800C HI decomposes ate 500C. This is the least stable and can act as a strong reducing agent.
Test for halides

(1) Acidify with nitric acid (2) Add aq. Silver nitrate White precipitate (silver chloride) Chloride ion Cream precipitate (silver bromide) Bromide ion Yellow precipitate (silver iodide) Iodide ion (3) Add NH3 (aq) White precipitate (silver chloride) dissolves in dilute colourless solution Cream precipitate (silver bromide) dissolves in excess colourless solution Yellow precipitate (silver iodide) doesnt dissolve Another test is with concentrated H2SO4: (1) With ClNaCl + H2SO4 NaHSO4 + HCl (white fumes) (2) With Br- and IH2SO4 is an oxidizing agent and oxidize HBr and HI into Br2 and I2, and their colours can be seen. With HBr, sulphuric acid is reduced by HBr into SO2 NaBr + H2SO4 NaHSO4 + HBr 2 HBr + H2SO4 H2O + Br2 + SO2 (Br2 is an orange vapour) With NaI, sulphuric acid is reduced by HI into SO2, S and H2S NaI + H2SO4 NaHSO4 + HI 2 HI + H2SO4 2 H2O + I2 + SO2 6 HI + H2SO4 4 H2O + 3 I2 + S 8 Hi + H2SO4 4 H2O + 4 I2 + H2S

Disproportionation reactions of chlorine


This happens in the reactions of chlorine with sodium hydroxide. These depend on the temperature: With cold dilute aq. NaOH, a mix of Cl- and ClO- (chlorate ions) is formed. Cl2 + 2 NaOH (aq) NaCl (aq) + NaClO (aq) + H2O This is disproportionation, in which chlorine is oxidized and reduced at the same time.

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This reaction is used to produce bleach which is HClO, chloric acid. It is a solution of NaCl and NaClO in a 1:1 mole ratio. With hot concentrated aq. NaOH, forms Cl- and Chlorate (v) (ClO3-) ions: 3 Cl2 + 6 NaOH (aq) 5 NaCl + NaClO3 + 3 H2O

Purification of drinking water


When Cl2 gas is used to purify drinking water, disproportionation occurs again to make HCl and HClO. Cl2 + H2O HCl + HClO The HClO (chloric acid) decomposes into HCl and O which kill the bacteria.

Uses of halogens
Cl2 and Cl2 (aq) are used as oxidizing agents, bleaches, treating drinking water and treating swimming pool water. Also used in the manufacture of various chemicals like chloroethene and CFCs which are used as fire extinguishers and are vital constituent of artificial blood. Solvents that contain chlorine such as di-chloromethane are used to dissolve fats and oils. Fluorine is used to make CFCs, PTFE (polytetrafluoroethene) which is used as a lubricant, a coating for non-stick pans, electrical insulation and in water proof clothing. Fluoride ions are used to prevent tooth decay. Hydrofluoric acid is used in etching glass. Bromochlorodifluoromethane is sued in fire extinguishers. Silver bromide is used in photographic film. Iodine is an essential part of our diet, and an imbalance causes thyroid problems. A solution of iodine is sometimes used as an antiseptic.

END OF LESSON

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Chapter 14 (AS-Level)
Nitrogen and Sulphur Nitrogen
It exists as a diatomic molecule.

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The triple bond is of great strength. The bond enthalpy is 945 kJ/mol, which makes breaking the triple bond very difficult. There are only a few of nitrogens reactions. In the upper atmosphere during a thunder storm, in which O2 react with N2 In an internal combustion engine N2 + O2 2 NO Followed by: 2 NO + O2 2 NO2 Nitrogen is converted to ammonia in the Haber process N2 + 3 H2 2 NH3 Atmospheric nitrogen is fixed by bacteria in the soil and root nodules of plants as nitrate ions.

Ammonia and ammonium compounds


Ammonia is a base, forming ammonium ions NH3 + H+ NH4+ Ammonium compounds such as ammonium sulphate (NH4)2SO4 are ionic salts and when heated with a base give off ammonia (NH4)2SO4 + 2 NaOH Na2SO4 + 2 H2O + 2 NH3 2 NH4Cl + CaO CaCl2 + H2O + 2 NH3

Industrial importance of ammonia and other compounds of nitrogen


Nitrogen extracted from liquefied air is used to make ammonia in Haber process Nitrogen is used as an inert atmosphere in food storage and some welding applications Ammonia is used by itself as a fertilizer by pumping it directly into the soil Ammonia can also be converted into ammonium sulphate (NH4)2SO4, ammonium nitrate (NH4NO3) or urea CO(NH2)2 which each is used as a fertilizer NH3 + HNO3(aq) + Heat NH4NO3(aq)

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2 NH3 + CO2 + Heat CO(NH2)2

Nitric acid manufacture


Ammonia is oxidized by air using a platinum catalyst at 900C A series of reaction involving NO and NO2 and dissolving the product in water Overall reaction: NH3 + 2 O2 HNO3 + H2O Nitric acid is used to make ammonium nitrate (fertilizer and explosives), nylon and TNT

The use of nitrate fertilizers


Nitrate fertilizers contain nutrients plant need to grow good and produce a good yield These fertilizers replace the lost ions in the soil Synthetic fertilizers contain ammonium nitrate, ammonium phosphate and potassium chloride

Environmental consequences of thee use of fertilizers


If too much fertilizer is applied to the soil, rainfall takes these dissolved nitrates into the water courses and drain into lakes and rivers. This is called leeching. When in the rivers, nitrates encourage the overgrowth of aquatic plants and algae. The algae soon cover the surface of the water, restricting the amount of light reaching the aquatic plants, so decreasing the amount of oxygen in the water. When the algae die, dissolved oxygen is used up and fish die. This is called eutrophication. The nitrates are very difficult to remove from the water and can cause illness in babies.

Nitrogen oxides in the atmosphere


High temperatures in internal combustion engines make nitrogen and oxygen to react together, producing NO and NO2. Other compounds like CO, CO2, SO2, and unburned hydrocarbons are also produced from exhausts. Catalytic converters are used to remove these compounds.

Sulphur
SO2 in the atmosphere
SO2 and oxides of nitrogen contribute to acid rain, which is a mix of nitric and sulphuric acids Reactions that lead to the formation of acid rain are: SO2 + NO2 SO3 + NO 2 NO + O2 2 NO2 Sulphur trioxide dissolves in the rain to make sulphuric acids SO3 + H2O H2SO4 NO2 dissolves with O2 in rain to make HNO3 2 NO2 + O2 + H2O 2 HNO3 These acids fall with the rain forming acid rain, which damages buildings, cars, trees, metals, etc. Reducing SO2 emissions are done by treating natural gas and crude oil to remove sulphur, which is used to make sulphuric acid.

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Exhaust gases from power stations are passed in CaO or CaCO3 to remove SO2 to form CaCO4

The contact process


Sulphuric acid is manufactured in the contact process. It includes equilibrium. (1) Sulphur is burnt in air to make SO2 S + O2 SO2 The sulphur comes from natural deposits or is recovered from natural gas or crude oil. SO2 can also be extracted from the roasting of sulphide ores during the extraction of some metals like zinc: 2 ZnS + 3 O2 2 ZnO + 2 SO2 (2) SO2 and O2 are passed over a heated V2O5 catalyst to make SO3 2 SO2 + O2 2 SO3 H= -96 kJ/mol Conditions: - 400C to 600C because catalyst is ineffective below 400C - Pressure just above atmospheric pressure In order to increase the yield of the SO3, excess of air is used to drive the equilibrium to the right. 4 beds of V2O5 are used. The catalyst raises the temperature of the gases so the mix is cooled before being passed into the next bed, which drives the equilibrium to the right. (3) SO3 is passed into 98% H2SO4 where it dissolves. Water is added to the solution to keep the concentration at 98%. The H2SO4 is removed regularly.

Sulphur dioxide in food preservation


SO2 is used by itself or as a sulphite to preserve food SO2 + H2O H2SO3 (aq) SO2 and suphites inhibit the growth of bacteria, yeasts, etc. and are reducing agents, so reduce the rate of oxidation of food. They are used to prevent the spoilage of dried fruit, dehydrated vegetables, fruit juices and sausages.

END OF LESSON

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Chapter 15 (AS-Level)
Introduction to Organic chemistry
containing other elements in addition to carbon and hydrogen.

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Organic chemistry is the study of compounds containing hydrogen and carbon and of compounds

Why are there many different carbon compounds? This is mainly due to: Carbon readily bonding to itself and to most other elements including metals (organometallic) Carbon can bond in a variety of ways giving rise to chains, rings and cages. Compounds that only contain carbon and hydrogen are called hydrocarbons. They are classified as aliphatic or aromatic. Aromatic compounds contain one or more arene rings. They have distinctive, usually pleasant smells. All the other organic compounds are aliphatic. For example, all alkanes and alkenes are aliphatic and benzene is an aromatic compound.

Types of formulae
There are some forms of formulae to remember: Molecular formula: it simply shows the number of atoms of each element present in the molecule. For example, hexane is C6H14 General formula: it may be written for a series of compounds. For example, for alkanes, it is CnH2n+2, where n is the number of carbon atoms Structural formula: it shows how the atoms are joined together in a molecule. For example, in hexane, it is CH3CH2CH2CH2CH2CH3 Displayed formula: shows all the bonds and all the atoms For example hexane,

Skeletal formula: shows all the bonds and all the atoms. Again, for example, hexane,

Three dimensional formula: gives you the best representation of a molecule.

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Functional groups
Each group of atoms that becomes attached to carbon has its own characteristic set of reactions. Each functional group gives rise to a homologous series which are molecules with the same functional group but with different lengths of carbon chains. For example, the functional group (-OH), gives rise to the homologous series of alcohols. They all have similar chemical properties. A general formula may be written for the aliphatic alcohols which is CNH2N+1OH. Some examples of functional groups are: Class of functional groups Alkenes Structure of functional groups Name of example Structural formula of example CH2=CH2

Ethene

Arenes

Benzene

Halogenoalkanes Alcohols and phenols Aldehydes

-X, where X= F, Cl, Br, I -OH

Chloromethane Methanol, phenol Ethanal

CH2Cl CH3OH, C6H5OH CH3CHO

Ketones

Propanone

CH3COCH3

Carboxylic acids

Ethanoic acid

CH3COOH

Esters

Ethyl ethanoate

CH3COOC2H5

Acyl chlorides

Ethanoyl chloride

CH3COCl

Amines Amides

-NH2

Methylamine Ethanamide

CH3NH2 CH3CONH3

Nitriles

-C N

Ethanenitrile

CH3CN

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Naming organic compounds
There are two way of naming organic compounds: Common names Systematic names (IUPAC names) Prefix Side chain, with numbers Stem Derived from the longest carbon chain of alkane. E.g. Methane, ethane, etc. Suffix Indicates functional groups. E.g. Ane, ene, al, ol, one, oic acid.

Basic rules for naming hydrocarbons: 1. The number of carbon atoms in the longest unbranching chain provides the stem of the name. They are named by adding ane to the stem. Molecular formula # of C atoms in Stem Name longest chain CH4 1 MethMethane C2H6 C3H8 C4H10 C5H12 C6H14 2 3 4 5 6 EthPropButPentHexEthane Propane Butane Pentane Hexane

2. Branched alkanes are named the same way in (1). The name is given to the longest unbranching carbon chain. It is then prefixed by the names of the shorter side-chains. The stem names are used with the suffix yl. For example, CH3- is methyl group (alkyl group). The position of the alkyl group is indicated by the number of the carbon atom that the alkyl group is on. Numbering starts from the end that produces the lowest possible numbers for the side-chains. For example, the following is 2, methylpentane.

3. Each side chain must be included in the name. If there are identical side-chains, the name is prefixed with di-, tri, tetra-, etc. For example, 2,2,3-trimethyl- indicates that there are three methyl groups, two on carbon 2 and one on carbon 3. If there are different alkyl groups, they are placed in alphabetical order. For example, 3-ethyl-2-methylpentane. 4. Compounds that have a ring of carbon atoms, the stem is prefixed by cyclo-. For example, cyclopentane is:

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5. In alkanes where there is an alkene or arene group: Alkene: ethene =

Arene: benzene

Displayed formula

Skeletal formula

The hydrocarbons with one double bond are called alkenes. The position of the double bond is indicated by the lower number of the two carbon atoms involved. This number is placed between the stem and the ene. For example, CH3CH=CHCH3 is but-2-ene. The simplest arene is benzene. When one alkyl group is attached to a benzene ring, a number is not needed because all the carbon atoms are equivalent. Two or more groups will require a number. For example:

Methylbenzene

1,2-dimethylbenzene

1,2,3-trimethylbenzene

6. In halogeno compounds, the name is the same as alkyl- substituted alkenes or arenes. CH3CH2CHBrCH3

2-Bromobutane

1,3-dichlorobenzene

7. In aliphatic alcohols and ketones are named in a similar way to alkenes. CH3CH2CH2OH CH3CH2COCH3CH3 Propan-1-ol Pentan-3-one

In aliphatic aldehydes and carboxylic acids, no numbers are needed. CH3CH2CHO CH3CH2COOH Propanal Propanoic acid

8. In amines, use alkyl or aryl prefix followed by the word amine. For example, CH3CH2NH2 is ethylamine.

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Organizing organic reactions


There are several organic reactions, which include:

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Acid-base reactions, for example, Ethanoic acid reacts with sodium hydroxide to form sodium ethanoate and water: CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l) Redox reactions, for example, between ethanol and oxygen: CH3CH2OH (aq) + O2 (g) CH3COOH (aq) + H2O (l) Substitution reactions, which involves replacing an atom by another atom. For example, the bromine atom in bromoethane is substituted by the OH group to form ethanol when it is warmed with sodium hydroxide: CH3CH2Br (l) + OH- (aq) CH3CH2OH (aq) + Br- (aq) Addition reactions, which involve 2 molecules combining to make only one new molecule. For example, if ethene and steam is passed over a hot phosphoric acid catalyst, ethanol is produced: CH2=CH2 (g) + H2O (g) CH3CH2OH (g) Elimination reactions, which involve the removal of a molecule from a larger one. For example, is ethanol is passed over a hot catalyst of pumice, a water molecule is eliminated: CH3CH2OH (g) CH2=CH2 (g) + H2O (g) Hydrolysis reactions involve breaking covalent bonds by the reaction with water. For example, when bromoethane is mixed with water, ethanol is formed along with hydrogen bromide: CH3CH2Br (l) + H2O (l) CH3CH2OH (aq) + HBr (aq)

Reaction mechanisms
A balanced chemical equation includes no information about the reaction pathway. The reaction pathway includes details of the intermediate chemical species which exist between the reactants and products. The activation energy is the energy needed to form these transient species. Catalysts increase the reaction rate by providing an alternative pathway for the reaction with lower activation energy. If a reaction pathway with lower activation energy is found, more molecules will have sufficient energy to react. Catalysts take part in the reaction mechanism but remain unchanged at the end of the reaction so they dont appear in the chemical equation.

Breaking bonds in different ways


A covalent bond consists of a pair of electrons between 2 nuclei in which they are attracted to the nuclei. This binds the 2 nuclei together. Covalent bonds can be broken in many ways. For example, if HCl is broken into H and Cl atoms, each atom takes one electron from the covalent bond. Atoms with unpaired electrons are called free radicals. When a covalent bond is broken to form 2 free radicals, the process is called homolytic fission. The energy for this process is usually provided by UV light or high temperature. Unpaired electrons are represented by a dot.

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Alternatively, a covalent bond may be broken so that one element takes both covalent bond electrons. For example, HCl would form hydrogen and chloride ions: HCl H+ + ClThe more electronegative element takes both the electrons. When a covalent bond is broken to form 2 oppositely charged ions, the process is called heterolytic fission. The bond in the HCl breaks heterolyticly when the gas dissolves in water to form hydrochloric acid. The movement of the two electrons is shown by a curly arrow. For example, when HCl dissolves in water:

Another example is the heterolytic fission of bromomethane:

Positively charged ions that contain carbon are called carbocations. A negatively charged ions containing carbon is called a carbanion. Free radicals, carbocations and carbanions are all highly reactive species. They react with molecules, causing covalent bonds to break and new covalent bonds to form. Carbocations and carbanion are electrophiles and nucleophiles respectively.
An electrophile is an electron-loving (and an electron-poor) species and is a proton acceptor and is attracted to electron-rich molecules, leading to the formation of a new covalent bond between the electrophile and thee molecule.

A nucleophile (nucleus-lover) is an electron-pair donor which is attracted to an atom with a partial positive charge, leading to the formation of a new covalent bond between the nucleophile and the molecule under attack.

Isomerism
Isomers have the same molecular formula but a different structural formula. Isomerism is due to a number of reasons, which include the ability of carbon being able to bond to itself and to most other carbon atoms in the periodic table.

Structural isomerism
Structural isomerism describes the situation where chemicals of the same formula behave differently because the structures are the same. For example, the atoms of butane can be put together in 2 ways, which is it has 2 isomers.

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H
H H C H H C H H C H H C H H

H C C H

H C H H H

C H H

Stereoisomerism
In stereoisomerism, the same atoms are joined to each other in different spatial arrangements. Geometric and optical isomerism are two types of this stereoisomerism.
Geometric (or cis-trans) isomerism

The atoms on either side of a carbon-carbon single bond can rotate freely, but the atoms around a carbon=carbon double bond cannot. For example, but-2ene, CH3CH=CHCH3 has 2 cis-trans isomers.

Cis-but-2-ene

Trans-but-2-ene

Optical isomerism
The simplest form of optical isomerism occurs when a carbon atom is joined to four different groups. The groups can be arranged in 2 different ways and the 2 isomers formed are mirror images of each other, which cannot be superimposed. These two optical isomers are also chiral molecules, which are molecules which are mirror images and cannot be superimposed. Optical isomerism is sometimes referred to as chirality. The carbon atom in the centre which carries the four different groups is called the chiral centre. Optical isomers, like other isomers, have the same molecular formula. As stereoisomers, they have the same atoms and the same bonds between the atoms. However, here, the bonds are arranged differently in space. For example, the molecule CHBrClF provides a good example of optical isomerism.

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To display the optical isomers, we need to use three-dimensional formula, in which the dotted line in the middle shows a mirror plane:

If the right hand molecule is rotated around the C-Cl bond, it produces:

The atoms Cl, C and F are in the same spatial position, but the H and Br are interchanged. If the two isomers are placed over each other (superimposed) they dont match. We say that they are non-superimposable. The key feature of a chiral centre in an organic molecule is that it has 4 different groups attached to it. The chiral centre in this molecule (Chloro-fluoro-bromo-methane) is labeled with a small star.

END OF LESSON

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Chapter 16a (AS-Level)


Hydrocarbons: Alkanes The physical properties of alkanes
The homologous series of the alkanes have the following properties:

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They have a general formula of CNH2N+2 They are non-polar molecules with only C-H and C-C bonds All the C-C bonds are single bonds so the alkanes are described as saturated hydrocarbons The atoms in the alkanes are held together by orbitals, which forms the axis between the 2 carbon nuclei and is formed by the overlap of 2 atomic -orbitals The 2 electrons in the (sigma) orbital attract both nuclei, binding them together in a bond The bond lies between the carbon atoms and either a hydrogen and carbon atoms. All the bond angles are 109.5 The atoms in the molecule can rotate freely about each C-C bond. This freedom to rotate gives great flexibility to the alkane chains.

The physical states of the alkanes at room temperature and pressure changes form gases to liquids to solids as the number of carbon atoms in the molecule increases. The volatility of the alkanes decreases as the number of the carbon atoms increases. The below table shows the boiling points for pentane and isomers of pentane: Alkane Pentane Structural formula CH3CH2CH2CH2CH3 Boiling point (K) 309 Space filling model

2-methylbutane

301

2,2-dimethylpropane

283

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As the number of branches in the chain increases, the boiling point decreases. All the isomers have the same number of atoms, so the trend cannot be explained using the number of electrons. As the isomers become more branched, the overall shape of the molecule becomes from the long balloon shape of pentane to the spherical shape of 2,2-dimethylpropane. The long balloon shape of pentane allows it to get closer to other pentane molecules than 2,2-dimethylpropane. The intermolecular forces increase when the molecules can approach each other and this is the case with pentane, which is way it has a higher boiling point than the other isomers as they cannot approach each other enough.

Chemical properties of alkanes


Combustion in air
Alkanes make excellent fuels. Complete combustion in air produces carbon dioxide and water. For example, the combustion of butane: C4H10 (g) + 6 O2 (g) 4 CO2 (g) + 5 H2O (g) The incomplete combustion of butane in an insufficient amount of oxygen produces carbon monoxide and water instead of carbon dioxide: C4H10 (g) + 4 O2 (g) 4 CO (g) + 5 H2O (g) Carbon monoxide is a toxic gas as it has no smell and colour and readily bonds to the iron groups of haemoglobin in the blood. This causes the haemoglobin to become unable to carry oxygen which may cause death in serious cases.

The substitution reaction of alkanes


Alkanes are inert compounds as they are non-polar. The carbon and hydrogen in the alkanes have very similar electronegativities and so they are non-polar. This also means that they are not attacked by common chemical reagents like acids, alkalis, water, etc. which are highly polar, and initiate the reaction by their attraction to the polar groups. These polar reagents dont react with the alkanes. Some non-polar reagents will react with the alkanes. These include the group IV elements chlorine, bromine, etc. that will react with alkanes under ultraviolet light, which will substitute the hydrogen atoms in the alkane with halogen atoms. For example, when chlorine is mixed with methane under UV light, chloromethane is formed and hydrogen chloride gas is evolved: CH4 (g) + Cl2 (g) CH3Cl (g) + HCl (g) This is a photochemical reaction as it requires UV light to begin. Further substitution is possible, in turn producing dichloromethane, trichloromethane and tetrachloromethane.

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The substitution mechanism

The sequence of the stages in a reaction is called the reaction mechanism. In this reaction, energy from ultraviolet light has to be absorbed to break the Cl-Cl bond. This is called photodissociation. Homolytic fission occurs and 2 free radicals of chlorine form. As homolytic fission of chlorine has to occur first, so it is the initiation step.

The reaction of a chlorine free radical with a methane molecule produces hydrogen chloride and a methyl free radical.

A methyl radical can react with a chlorine molecule to make chloromethane and new chlorine radical.

These 2 steps enable the reaction to continue. In the first step, a chlorine radical is used up. The second step releases a new chlorine free radical allowing the repetition of the first step. The reaction will continue as long as there is a supply of methane molecules and chlorine free radicals. These two steps make up a chain reaction and are known as the propagation steps of the reaction. When the reagents are used up, no more chloromethane and hydrogen chloride are formed. The reaction can end in two ways: Either that the chlorine free radicals recombine to make chlorine molecules,

Or; The methyl free radicals recombine to make an ethane molecule These termination steps will remove the free radicals and disrupt the propagation steps and stopping the chain reaction. The following steps make up the reaction mechanism: Initiation, 2 propagation steps, And one of the termination steps As the reaction is a substitution reaction involving free radicals, it is called a free-radical substitution.

END OF LESSON

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Chapter 16b (AS-Level)


Hydrocarbons: Alkenes Physical properties of alkenes
Simple alkenes are hydrocarbons that contain one C=C double bond. The simplest is ethene, CH2=CH2. The general formula of the homologous series of the alkenes is CnH2N.

Bonding in alkenes: and bonds


Electrons in molecules may occupy and orbitals. In double bonds, the first bond involves an overlap of atomic orbitals directly in between the nuclei of the two atoms:

This is known as a -bond. All single covalent bonds are -bonds. The second bond, however, cannot bond in the same place. Instead two p-orbitals overlap above and below the internuclear axis:

This is known as a -bond. All double covalent bonds consist of one -bond and one -bond, in which the -bond exists on each side of the -bond. For example, ethene has one sigma bond and one pi bond

Compounds which contain -bonds, such as ethene, are called unsaturated hydrocarbons. The term unsaturated indicates that the compound will combine by addition reactions with hydrogen and other chemicals, losing its double bond.

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Saturated compounds contain only one C-C single bond. Polyunsaturated compounds have more than one C=C double bond.

Cis-trans isomerism
Many alkenes exhibit cis-trans isomerism. It is caused by the restricted rotation about a carboncarbon double bond. It arises when the carbon atoms on both sides of the bond are attached two different groups. E.g. but2-ene has two geometrical isomers:
CH3 CH3
CH3

H C C
CH3

C H

C H
H

These two isomers cannot be interconverted without breaking the -bond. In cases where both C atoms are attached to one hydrogen atom, it is possible to distinguish the isomers by a simple prefix. If both hydrogen atoms are on the same side of the molecule, the prefix cis- is used. If the hydrogen atoms are on different sides of the molecule, the prefix trans- is used.

Cis-but-2-ene

Trans-but-2-ene

It is only possible to name geometrical isomers using cis- and trans- prefixes if both carbon atoms are attached to a hydrogen atom. Note that molecules which show geometrical isomerism always have two specific structural features: There is a carbon-carbon double bond; Both the carbon atoms are attached to two different groups.

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Polymers of ethene can also be exhibit cis-trans isomerism. For example, there are two polymers of butene: o Cis-poly(but-2-ene):

o Trans-poly(but-2-ene):

Characteristic reactions of alkenes


Most reactions involving alkenes involve the breakage of the -bond. It is weaker than the -bond and can react with a variety of reagents.

Addition reactions to the double bond


The characteristic reaction of an alkene involves a simple molecule such as hydrogen, water or a halogen, which joins to the double bond to form a single product.
Addition of hydration

This converts the unsaturated alkene to a saturated alkene. Hydrogen gas and a gaseous alkene are passed over a finely divided nickel catalyst supported on an inert material. For example, the addition of hydrogen to ethene: CH2=CH2 (g) + H2 (g) CH3-CH3 (g)
Addition of halogens

When an alkene such as propene is bubbled through a solution of bromine at room temperature, the bromine solution is rapidly decolourized. This reaction doesnt need UV light to occur. The bromine joins to propene to form 1,2-dibromopropane: CH3CH=CH2 + Br2 CH3CHBrCH2Br Chlorine and iodine produce similar reactions as bromine. This reaction is also a test for unsaturated hydrocarbons like ethene.
Addition of hydrogen halides

Hydrogen halides also react with alkenes in addition reactions. Ethene produces chloroethane when it is bubbled through concentrated hydrochloric acid:

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CH2=CH2 (g) + HCl (aq) CH3CH2Cl (l) The reactivity of the hydrogen halides increases from HF to HI, following the order of decreasing bond energy. Alkenes such as propene can give rise to 2 different products.
Addition of steam

These reactions convert alkenes into alcohols. Steam and an alkene are mixed together in the presence of phosphoric acid to make an alcohol. A temperature of 600K and a pressure of 6MPa are used. For example, the addition of steam to ethene produces ethanol: CH2=CH2 (g) + H2O (g) CH3CH2OH
Fission

Fission is the breaking of bonds. It can be of two types: o Homolytic fission, in which a covalent bond is broken and the 2 atoms around the bond would each take one electron. This normally happens in non-polar molecules such as Cl2. This process produces 2 free radicals:

The free radicals are noted by a dote representing an electron next to the free radical. The free radicals are very reactive, have high energy and are very unstable. o Heterolytic fission, in which one atom in the covalent bond takes both electrons, becoming a negative ion and leaving a positive ion. This is process happens in polar molecules, including the ones that have induced poles. For example, in the electrophilic addition of bromine to alkenes, in which the bromine molecule becomes polarized due to the -bond of the alkene.

The mechanism of the reaction; how the reaction proceeds


Bromine and ethene are non-polar reagents. The bromine molecule becomes polarized when near to a region of negative charge, like the -bond of ethene. In the first stage of the reaction, the -bond breaks and the bromine molecule undergoes heterolytic fission, in which one of the bromine atoms takes all the electrons, becoming a negatively charge ion and the other atom becoming positively charged. The positive ion becomes attached to both carbon atoms, with the positive charge being found on the bromine atom. A bromonium ion is formed, which is a carbocation.

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The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction.

In this reaction, the polarized bromine behaved as an electrophile, therefore the reaction is called the electrophilic addition of bromine.

Reactions of alkenes with manganate (VII) ions


Alkenes undergo a different type of reaction with manganate (VII) ions, depending on the conditions: o With cold, acidified or alkaline dilute potassium manganate (VII) ions, the alkenes react readily at room temperature. The purple colour disappears and a diol is formed. CH2=CH2 + H2O + [O] HOCH2CH2OH o With hot, acidified solution of potassium manganate (VII), any diol produced is split into fragments which are further oxidised into ketones or carboxylic acids. o Ethene oxidises into ethan-1,2-diol and then further oxidised into carbon dioxide

o Propene will give Ethanoic acid and carbon dioxide

o 2-methyl prop-1-ene will give Propanone and carbon dioxide

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Polymerisation of alkenes
Alkenes can be made to join together in the presence of high pressure and a suitable catalyst. This is known as addition polymerisation.

C n

The product of this addition process is a very long hydrocarbon chain. This is known as a polymer. Since it is a product of an addition reaction (unlike some other polymers) it is known as an addition polymer. Since it is made from an alkene it is known as a poly(alkene). Poly(alkenes) are saturated, like alkanes. They are therefore unreactive. Addition polymers can be made from any alkene:
H H n H C C H H C H C H n H

Eg ethene

poly(ethene)

Poly(ethene) is most widely used in plastic shopping bags.


H H n H C C H H H n CH3 C C CH3

E.g. propene

poly(propene)

Poly(propene) is used in biros, straws and plastic food containers. It can be recycled commercially.

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H H n H C C H H H n C2H5 C C C2H5

E.g. but-1-ene

poly(but-1-ene)

H H n CH3 C C H CH3 C

CH3 C n

CH3 H

Eg but-2-ene

poly(but-2-ene)

CH3 H CH3 n CH3 C C H CH3 H H C C n

E.g. 2-methylpropene

poly(2-methylpropene)

END OF LESSON

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Chapter 17 (AS-Level)
Halogenoalkanes (Alkyl halides) General

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They have a general formula of CNH2N+1X, where X is the halogen atom. They are known also as alkyl halides. They are hydrocarbons containing a halogen atom, joined to one or more carbon atoms in a chain. They are named by prefixing fluoro, Chloro, bromo and iodo to the name of the alkane, along with the number of the carbon atom it is attached to.

Classification of halogenoalkanes
1. Primary halogenoalkanes, e.g. 1-chlorobutane, have a halogen atom covalently bonded to a carbon atom which has only one another carbon atom bonded to it.

2. Secondary halogenoalkanes, e.g. 2-chlorobutane, have a halogen atom covalently bonded to a carbon atom which has 2 other carbon atoms bonded to it.

3. Tertiary halogenoalkanes, e.g. 2-chloro-2-methylpropane, in which the halogen atom is covalently bonded to a carbon atom which has bonds with 3 other carbon atoms.

Physical properties
They are volatile liquids that dont mix with water.

Nucleophilic substitution
All nucleophilic substitution reaction of alkyl halides involves the breaking of the bond between the carbon and the halogen atom.

The polarity of the carbon-halogen bond


With the exception of iodine, all halogens are more electronegative than carbon. This means that the electron-pair in the C-X (X for halogen) bond will be dragged over to the halogen atom end, making a negative pole (-) at the halogen and a positive pole at the carbon atom (+).

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The strength of the C-X bond


Some bond energies of different C-X bonds: Bond C-H Bond energy (kJ/mol) 413 Bond C-F C-Cl C-Br C-I Bond energy (kJ/mol) 467 346 296 228

In all nucleophilic substitution reactions, the carbon-halogen bond must be broken. The harder it is to break, the slower the reaction. The bond energies decrease from Cl to I, so I is the most reactive.

Nucleophilic substitution in primary alkyl halides (SN2)

A nucleophile is a species that loves positive charges. They can be negative ions or have a strong charge on their molecules. Examples include:

Hydroxide ion

Cyanide ion

Water

Ammonia

These contain at least one lone pair of electrons, or a very electronegative atom carrying the charge. With reaction with halogenoalkanes, for example, bromomethane, there is a polar bond between the Br and the C atoms:

If a nucleophilic ion approaches the molecule, for example, OH- ion, it will be attracted to the carbon atom and repelled by the bromine atom.

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It moves towards the carbon atom and begins to make a dative bond with it. The electrons in the C-Br bond start to be pushed towards the Br atom. This causes the Br atom to get expelled as a Br ion.

This is called SN2 reaction. The S for substitution, N for nucleophilic and 2 because the initial step of the reaction involved 2 species.

Nucleophilic substitution in tertiary halogenoalkanes (SN1)


Why is a different mechanism necessary for tertiary alkyl halides? When a nucleophile attacks a primary alkyl halide, it approaches the carbon atom from the ide away from the halogen atom. With tertiary alkyl halides, this is impossible as the backside is cluttered with CH3 groups.

Since any other approach is denied by the bromine atom, the reaction has to go by an alternative route or mechanism. The reaction happens in two stages: 1. A small proportion of the alkyl halide ionizes into a carbocation and a halide ion (in this case it is Bromine ion).

This reaction is possible because the tertiary carbocations are more stable that secondary or primary alkyl halide carbocations. However, this reaction is slow. 2. However when the carbocation is formed, it would react immediately with the nucleophile as the nucleophile is attracted to it.

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Because the reaction involves only one species, it is described as SN1 reaction.

Hydrolysis
If an alkyl halide is heated under reflux with a solution of NaOH, the halogen atom is replaced by OH and an alcohol is formed. The solvent is usually a 50/50 mix of ethanol and water, as both hydrocarbons and other watersoluble substances are soluble in it. The reaction is the same as before in nucleophilic substitution:

The same hydrolysis happens with water but it is slower: CH3-Br + H2O CH3OH + HBr The mechanism of the reaction with water: 1. Nucleophilic substitution:

The reaction is slow as water isnt a good nucleophile as it does not carry a charge. 2. Another water molecule removes one of the hydrogen atoms, to give an alcohol and an oxonium ion:

3. The oxonium ion and the bromine ion from step 1 form hydrobromic acid (HBr):

The above is for primary alkyl halides. For tertiary alkyl halides, the reaction is the same as with normal SN1 reactions.

Reaction with ammonia


If alkyl halides are mixed with an excess of ethanolic ammonia and heated under pressure, amines are formed. For example, bromoethane will form ethylamine: CH3CH2Br + NH3 CH3CH2NH2 + HBr Ethylamine is a primary amine.

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Reaction with cyanide ions

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When halogenoalkanes are heated under reflux with ethanolic sodium cyanide, nitriles are formed. For example: CH3CH2Br + NaCN CH3CH2CN +NaBr This reaction contains one more carbon atom. The mechanism is:

Because the mechanism involves collision between two species in the slow step (in this case, the only step) of the reaction, it is known as an SN2 reaction.

Elimination reactions
2-bromopropane is heated under reflux with a concentrated solution of sodium or potassium hydroxide in ethanol. Heating under reflux involves heating with a condenser placed vertically in the flask to avoid loss of volatile liquids. Propene is formed and, because this is a gas, it passes through the condenser and can be collected.

Everything else present (including anything formed in the alternative substitution reaction) will be trapped in the flask. The mechanism is: In elimination reactions, the hydroxide ion acts as a base - removing a hydrogen atom as a hydrogen ion from the carbon atom next door to the one holding the bromine. The resulting re-arrangement of the electrons expels the bromine as a bromide ion and produces propene.

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This is actually the elimination of hydrogen halide (in this case it is bromine) from the alkyl halide, leaving an alkane. The hydrogen halide reacts with the sodium ion present to form sodium bromide. This happens when a solution of pure alcohol with an alkali is used. This is because the rate of elimination is faster than the rate of nucleophilic substitution. At lower temperatures, the substitution reaction proceeds at a faster rate.

The uses of halogeno alkanes


CFCs are non-flammable and not very toxic. They therefore had a large number of uses. They were used as refrigerants, propellants for aerosols, for generating foamed plastics like expanded polystyrene or polyurethane foam, and as solvents for dry cleaning and for general degreasing purposes. Unfortunately, CFCs are largely responsible for destroying the ozone layer. In the high atmosphere, the carbon-chlorine bonds break to give chlorine free radicals. It is these radicals which destroy ozone. CFCs are now being replaced by less environmentally harmful compounds. Bromochlorodifluoromethane is used to stop extinguish fires. When combustible materials are ignited, free radicals are generated. These free radicals propagate many combustion reaction steps which produce even more free radicals. The high temperatures break the compound down, producing bromine free radicals, which react with the free radicals produced from the combustion of the flammable material, extinguishing the fire.
Problems with CFCs

CFCs are responsible for the depletion of the ozone layer. The high stability of the CFCs is one of the causes of the depletion of the ozone layer, which had enabled them to stay in the stratosphere a long time and build up there. When they reach the stratosphere they absorb ultraviolet light, which causes the photochemical dissociation of the carbon-chlorine compounds. CF2Cl2 (g) CF2Cl. (g) + Cl. (g) Very reactive chlorine free radicals are formed, which catalyse the decomposition of ozone into oxygen. 2 O3 (g) 3 O2 (g)

END OF LESSON

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Chapter 18a (AS-Level)


Hydroxy compounds Alcohols The different types of alcohols
There are three types of alcohols:

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1. Primary alcohols: In primary alcohols, the OH group is attached to a carbon atom which is attached to only one alkyl group (or no alkyl group as in methanol): Examples include: CH3CH2-OH Ethanol

CH3CH2CH2-OH Propan-2-ol

2. Secondary alcohols: In secondary alcohols, the OH group is attached to a carbon atom which is attached to 2 alkyl groups: Examples include:

Propan-2-ol

Butan-2-ol

3. Tertiary alcohols: In tertiary alcohols, the OH group is attached to a carbon atom which is attached to 3 alkyl groups: Examples include:

2-methylpropan-2-ol

2-methylbutan-2-ol

Physical properties
Some points to remember: The boiling points of the alcohols increase as the carbon chain increases in size The boiling points of the alcohols are higher than corresponding alkanes, which is due to: o Hydrogen bonding that occurs between OH groups of alcohols o Alkanes have no lone pairs so only Van der Waals forces present

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Solubility of alcohols in water (miscibility in water)

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Small chain alcohols are completely soluble in water. However, solubility falls as the length of the hydrocarbon tails of the alcohols increases. Once you get to 4 carbon atoms and beyond, the fall in solubility is noticeable. Smaller alcohols can form hydrogen bonds with the water molecules as well as the larger chain molecules, but thee bigger chain alcohols would be forcing their way between the water molecules, breaking the hydrogen bonds as the tail cannot have hydrogen bonds. The hydrocarbon tails only exert weak Van der Waals forces which are not enough to keep the liquids mixed.

Manufacture of alcohols
Ethanol is manufactured from the hydrolysis of ethene, which is the reaction of steam with ethene, in the presence of solid silicon dioxide coated with phosphoric acid. The reaction is reversible: CH2=CH2 (g) + H2O (g) Conditions: 300C 60-70 ATM H3PO4 acid catalyst CH3CH2OH (g)

Reactions of alcohols
Reactions in which the O-H bond is broken
Reaction with sodium

Metallic sodium reacts with ethanol in a less vigorous reaction than with water. It reacts readily to produce hydrogen gas and a colourless solution of sodium ethoxide (CH3CH2O-Na+). Sodium ethoxide is an alkoxide. 2 CH3CH2OH (l) + 2 Na (s) 2 CH3CH2ONa + H2 (g) If the solution is tested with phenolphthalein indicator, the solution turns pink, indicating a high pH. The reaction is used to: Indicate the presence of an OH group in alcohols Remove small traces of sodium safely

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Esterification

Esters are produced when carboxylic acids are heated with alcohols in the presence of a strong acid like sulphuric acid. The process is slow and reversible. The general equation for esterification is:

For example, the reaction of ethanol with ethanoic acid produces ethyl ethanoate:

Esters like ethyl ethanoate have fruity smells and are naturally found in fruits. Esters can also be formed from alcohols and acyl chlorides. Adding an acyl chloride to an alcohol is a vigorous exothermic reaction, which produces clouds of hydrogen chloride gas at room temperature. For example, if ethanoyl chloride is mixed with ethanol, ethyl ethanoate is formed along with HCl gas:

The reaction is reversible; equilibrium is well to the right as the HCl gas escapes and so more ester and HCl has to be produced, so it is written as irreversible.

Reactions in which the C-O bond is broken


Substitution to form halogenoalkanes

When ethanol is heated with concentrated sulphuric acid and sodium bromide, bromoethane is formed. Concentrated sulphuric acid and sodium bromide react to form hydrogen bromide and sodium hydrogen sulphate: NaBr (s) + H2SO4 (l) NaHSO4 (s) + HBr (g) With ethanol, HBr acts as a nucleophile, substituting the Br atom for the OH group of ethanol:

This reaction is a reverse of hydrolysis of an alkyl halide.

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For alkyl halides containing Cl or I, there are different ways of making them: Chloroalkanes can be made by reacting alcohols with phosphorous (III) chloride PCl3, phosphorous (V) chloride, PCl5 or SOCl2, sulphur dichloride oxide: CH3CH2OH + PCl5 CH3CH2Cl + HCl + POCl3 CH3CH2OH + SOCl2 CH3CH2Cl + HCl + SO2 Iodoalkanes can be made by warming an alcohol with a mixture of red phosphorous and iodine. PI3 is formed which then reacts with alcohol: 2 P + 3 I2 2PI 3 3 CH2OH + PI3 2 CH3I + P(OH)3

Reactions that involve the breaking of the C-C or C-H bonds


Mild oxidation

Oxidation is the addition of oxygen. The oxidizing agent used here is potassium dichromate(VI) acidified with dilute sulphuric acid. If oxidation occurs, the orange colour of potassium dichromate solution changes into a green solution containing chromate ions. With primary alcohols Primary alcohols can be oxidized into aldehydes or carboxylic acids, depending on the reaction conditions. Carboxylic acids are formed when aldehydes formed are oxidized further. Partial oxidation Aldehydes are produced if you use an excess of alcohol and if the aldehyde is distilled as it is formed (there is not enough oxidizing agent to oxidise the aldehyde). The reaction is: CH3-CH2-OH + [O] CH3-CHO + H2O Here the colour of the solution changes from orange to green. Full oxidation Here an excess of an oxidizing agent is used and the mixture is heated under reflux, making sure that no aldehyde can escape. CH3-CH2-OH + [O] CH3-CHO + H2O Then: CH3CHO + [O] CH3COOH

With secondary alcohols Secondary alcohols are oxidised into ketones only. For example, heating propan-2-ol with acidified potassium dichromate(VI), Propanone formed.

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With tertiary alcohols No reaction occurs, because the oxidizing agent has to remove one hydrogen from the OH group and another from the same carbon atom.

The dehydration of ethanol to give ethene This is a simple way of making gaseous alkenes like ethene. If ethanol vapour is passed over heated aluminium oxide powder, the ethanol is essentially cracked to give ethene and water vapour.

To make a few test tubes of ethene, you can use this apparatus:

It wouldn't be too difficult to imagine scaling this up by boiling some ethanol in a flask and passing the vapour over aluminium oxide heated in a long tube.

Uses of alcohols
Uses of ethanol
Drinks

The "alcohol" in alcoholic drinks is simply ethanol.

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Industrial methylated spirits (meths)

Ethanol is usually sold as industrial methylated spirits which is ethanol with a small quantity of methanol added and possibly some colour. Methanol is poisonous, and so the industrial methylated spirits is unfit to drink. This avoids the high taxes which are levied on alcoholic drinks (certainly in the UK!).
As a fuel

Ethanol burns to give carbon dioxide and water and can be used as a fuel in its own right, or in mixtures with petrol (gasoline). "Gasohol" is a petrol / ethanol mixture containing about 10 - 20% ethanol. Because ethanol can be produced by fermentation, this is a useful way for countries without an oil industry to reduce imports of petrol.

As a solvent

Ethanol is widely used as a solvent. It is relatively safe, and can be used to dissolve many organic compounds which are insoluble in water. It is used, for example, in many perfumes and cosmetics.

Uses of methanol
As a fuel

Methanol again burns to form carbon dioxide and water.

It can be used a a petrol additive to improve combustion, or work is currently being done on its use as a fuel in its own right.
As an industrial feedstock

Most methanol is used to make other things - for example, methanal (formaldehyde), ethanoic acid, and methyl esters of various acids. In most cases, these are in turn converted into further products.

END OF LESSON

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