UNIT 2 NOTES

TOPIC 1:ENERGETICS
Exothermic - a reaction where heat energy is transferred from the system to the surroundings.
Endothermic – a reaction where heat energy is transferred from the surroundings to the
system.
Enthalpy change – heat energy change measured at constant pressure.

ΔH=Hp-Hr
Standard conditions: 100kPa pressure and 298K temperature.

Enthalpy level diagrams

Energy profile diagram

Standard enthalpy change of reaction - It is the enthalpy change when the number of moles
indicated by a chemical equation is completely reacted under standard conditions of 298K and
100kpa pressure.
Standard enthalpy change of formation - Enthalpy change when one mole of a compound is
formed from its element in their standard states under standard conditions of 298K and 100
kpa pressure. (Enthalpy change of formation of a compound is a useful way of judging the
energetic stability of a compound. The more exothermic the enthalpy change of formation, the
more the energetic stability of the compound)
Standard enthalpy change of combustion - It is the enthalpy change when one mole of a
substance is completely burned in oxygen under standard conditions of 298K and 100kpa
pressure.
Standard enthalpy change of neutralization - It is the enthalpy change when one mole of water
is formed by the reaction between an acid and a base under standard condition of 298K and
100kpa pressure. (Standard enthalpy change of neutralization of a strong acid and a strong base
is always constant =-57.1 KJ/mol)
Standard enthalpy change of atomisation - It is the enthalpy change when one mole of gaseous
atoms is formed from the element in its standard state under the standard conditions of 298K
and 100kpa pressure.

Experimental determination of enthalpy change of combustion of a liquid: To find the

enthalpy change of combustion of a liquid, a known mass of the liquid is burned and the heat
energy released is used to heat a known volume of water.
The following procedure is used.
 A spirit burner containing the liquid being tested is weighed.
 A known volume of water is added to a copper can.
 The temperature of the water is measured.
 The burner is lit.
 The mixture is constantly stirred with the thermometer.
 When the temperature of the water has reached approximately 20°C above its initial
temperature, the flame is extinguished and the burner is immediately reweighed.
 The final temperature is measured.
Q) Explain why enthalpy change of neutralization of a strong acid and a strong base is always
a constant.
Ans) This is because, it is the enthalpy change of formation of one mole of water from H + and
OH- ions, which is always a constant (-57.1kJ/mol)

Q) Explain why the enthalpy change of neutralization of a weak acid and a weak base is less
exothermic than that of a strong acid and a strong base.
Ans) This is because a part of the heat liberated is used for complete ionization to occur since
weak acid and weak base is only partially ionized in aqueous solution

Experimental determination of enthalpy change of neutralisation:

 Wear safety glasses and a lab coat.
 Using a pipette fitted with a safety filler, place 25.0 cm³ of 1.00 mol dm-3 acid into an
expanded polystyrene cup.
 Measure the temperature of the acid.
 Using a pipette fitted with a safety filler, place 25.0 cm³ of the alkali (usually dilute
sodium hydroxide of a concentration slightly greater than 1.00 mol dm-³ (to make sure
all the acid is neutralised) into a beaker
 Measure the temperature of the alkali.
 Add the alkali to the acid, stir with the thermometer and measure the maximum
temperature reached.

Thermometric titration – a titration where the endpoint is indicated by a temperature change.

Heat capacity (C):- is the amount of heat required for an object to raise its temperature by 1K.
Its unit is J/K
Specific heat capacity (c):- is the amount of heat required to raise the temperature of 1kg or
(1g) of a substance by 1K. Its unit is Jkg-1K-1or Jg-1K-1

The amount of heat transferred is given by Q = mcΔT

Enthalpy change (molar enthalpy change):- is given by ΔH = Q/n where ‘n’ is the number of
moles of the fuel or the limiting reagent.
*For an increase in temperature in the reaction vessel (ΔT = +ve). ΔH should be-ve.
*For a decrease in temp.in the reaction vessel (ΔT = - ve), ΔH should be +ve.
*One way to measure the enthalpy change involves carrying out the chemical change in an
insulated container known as calorimeter.
Polystyrene cup is an excellent insulator and it has a very low specific heat capacity. Therefore,
to measure the enthalpy change in the lab, we can use a polystyrene cup.
The calorimeter used to determine the energy change during a reaction is known as bomb
calorimeter.
In a calorimeter, however good is the insulation, some heat is transferred to the surroundings
which adds an element of inaccuracy and unreliability to the results. The accuracy can be
improved by using a more sophisticated calorimeter.

Source of error and improvement:

 The main source of error in ΔH calculation is the heat loss to the surroundings. To
reduce this problem use more insulation (polystyrene cup with lid, draught shield etc)
 Make the reaction faster to minimize heat loss
 use pipette or burette for accurate measurements.

To calculate ΔT (using graphs)

 Take more than one initial reading → to ensure that the temperature of the solution is
the same as that of the room condition.
 Take series of temperature readings to avoid fluctuation in temperature (minimize
reading error)
 Allow cooling effect (more accurate temperature change)

For combustion reactions (sources of error)

 Loss of heat
 Incomplete combustion which produce CO and C (soot)

% Error calculation

Hess’s Law – the law states that the enthalpy change of a reaction is independent of the path
taken in converting reactants into products, provided the initial and final conditions are the
same in each case.
Bond enthalpy or bond energy is endothermic (unit KJ/mol)
Bond breaking → endothermic (+ve)
Bond forming → exothermic (-ve)

Enthalpy change calculated using bond enthalpy values are slightly different from the enthalpy
value obtained experimentally because:
1) Average value of bond energy taken from many different compounds is used
2) Bond enthalpy applies to substances in their gaseous state. Many reactions involve solids,
liquids or gaseous solutions. Therefore, there is an inaccuracy in the calculation.

Kinetic stability and thermodynamic stability (energetic stability)

 A reaction may be highly exothermic, yet nothing happens because the reaction rate is
very slow and the reactants are kinetically stable with respect to the products.
 A compound is said to be kinetically stable when the activation energy for the reaction is
very high.
 Some compounds are energetically unstable with respect to their elements, but they
don’t change at ordinary temperature and pressure, because their reaction rate is very
slow and the reactants are said to be kinetically stable.
 The combination of H2 and O2 is thermodynamically favored at ordinary temperature,
but these gases can be left together indefinitely at room temperature without
appreciable change. This is because, the reaction rate is very slow and the reaction to
take place, a catalyst is required.
O
 Consider the reaction, CH4(g) + 2O2(g)→ CO2(g) + 2H2O(l); ΔH = -890KJ/mol
In this reaction, the reactants CH4 and O2 are at a higher energy level than the
products. So, the reactants are thermodynamically unstable with respect to the
products and the reactants are kinetically stable due to high activation energy.
TOPIC 2: INTERMOLECULAR FORCES

London forces nature: A molecule is said to be

non-polar when the electron density is
symmetrically distributed throughout the
molecule. However, electron density fluctuates
over time. If at any time electron density
becomes unsymmetrical in a molecule, a dipole will
be generated and one end of the molecule becomes
partially negative and the other end becomes
partially positive. As a result an instantaneous dipole is
created. This instantaneous dipole induces a similar
polarity on a neighbouring molecule. The two dipoles
are arranged in such a way that they will interact
favourably with one another. It is this favourable
interaction that is responsible for the London force of
attraction between the two molecules.

Features of London forces:

1) It increases as the number of electrons in the
molecule increases.
Example: Boiling point of noble gases is in the order He<Ne<Ar<Kr<Xe<Rn . Here London force is
the only force of attraction between the molecules. The more the number of electrons, the
more the fluctuation in electron density and the greater the instantaneous and induced dipole
created. (B.p. of halogens is in the order F2<Cl2<Br2<I2<At2 same answer)
2) London force depends on the shape and size of the molecule. The more the points of contact
between the molecule, the greater the overall London force.
3) London force is always present between the molecules.

Permanent dipoles nature: If the molecules possess permanent dipoles, they will also interact
with one another. If the dipoles are aligned correctly, then there will be a favourable interaction
and the two molecules will attract one another.

*In a liquid, the random movement of the molecules is such that the dipoles are not always
aligned to produce a favourable interaction.
As a result, when averaged out, the interaction between permanent dipoles is usually much less
than the interaction between instantaneous and induced dipoles. The London force is the more
significant interaction between molecules.

* Induced dipoles are always aligned so that their interaction is favourable. This is not true for
permanent dipoles.

Hydrogen bond nature: Hydrogen bond is formed when the atom bonded to hydrogen has to be
more electronegative than hydrogen. There are two types of hydrogen bonding 1. Intermolecular
H bonding between different molecules and 2. Intramolecular H bonding within the same
molecule. H bonding is very significant when hydrogen is bonded to very small highly
electronegative atoms such as O, N and F.

Hydrogen bonding through oxygen:

The interaction is not just an extreme of dipole-dipole interaction. There is some partial bond
formation using the lone pair of electrons on the oxygen atom. Because the oxygen atom has
two lone pairs, it can form hydrogen bonds with two other water molecules. Like covalent
bonds H bonds are directional in nature.

Hydrogen bonding between two ethanol molecules

Hydrogen bonding through Nitrogen

All compounds containing an -N-H group can form intermolecular H bonds.
Hydrogen bonding through fluorine
The only fluorine compound with intermolecular hydrogen bonding is hydrogen fluoride.

Hydrogen bond an intermolecular interaction (in which there is some evidence of bond
formation) between a hydrogen atom of a molecule (or molecular fragment) bonded to an atom
which is more electronegative than hydrogen and another atom in the same or a different
molecule.

Intermolecular interactions and physical properties

The only significant intermolecular interaction between alkane molecules is the London force.
There are two reasons for the increase in boiling temperature with increasing molecular mass:
1) As molecular mass increases, the number of electrons per molecule increases and so the
instantaneous and induced dipoles also increase.
2) As the length of the carbon chain increases, the number of points of contact between adjacent
molecules increases. Instantaneous dipole-induced dipole forces exist at each point of contact
between the molecules, so the more points of contact there are, the greater the overall
intermolecular (London) force of attraction.

Alcohols: since they contain -O-H group, they can form intermolecular H bonds in addition to
London forces so they have higher boiling point when compared with equivalent alkanes.
Consider the case of methanol (CH3OH) and ethane (CH3CH3). Both molecules have similar chain
length and have same number of electrons. The boiling point of methanol is higher than that of
ethane. This is because of the hydrogen bonding that exists between the methanol molecule
which is not there in alkane. So more energy is required to separate the molecule.
The enthalpy change of vaporisation is a measure of the amount of energy that is required to
completely separate the molecules of a liquid and convert it into a gas at the same temperature. It
is, therefore, a direct measure of the strength of the intermolecular interactions. The greater the
enthalpy change of vaporisation, the greater the forces of attraction between the molecules.

Boiling point of hydrogen halides

The boiling point of hydrogen halides is in the order HF>HCl<HBr<HI . The high B.P. of HF is due
to the presence of strong hydrogen bond due to the high electronegativity of Fluorine. London
force is weaker in HF due to less number of electrons.

Boiling temperature of hydrides of group 5 is in the order NH3>PH3<AsH3<SbH3<BiH3 and boiling

temperature of hydrides of group 6 is in the order H2O>H2S<H2Se<H2Te<H2Po (Explanation same
as above)

Anomalous properties of water

Water has some anomalous properties. The following two are particularly important:
1) It has a relatively high melting and boiling temperature for a molecule with so few electrons.
2) The density of ice at 0°C is less than that of water at 0 °C.

Melting and boiling temperatures

The hydrogen bonds between water molecules are relatively strong. As a result, the overall
intermolecular forces of attraction in water are greater than would be expected from the number
of electrons (10) in the molecule.
Water, therefore, has an abnormally high melting temperature (0 °C, 273 K) and boiling
temperature (100 °C, 373 K) at 100 kPa pressure.
It is interesting to compare the boiling temperatures of water, ammonia and hydrogen fluoride.

Boiling point of HF < H₂O. In HF molecule, there is only one H - F bond, though there are 3
unshared pairs of electrons on fluorine atom. This means that there can be an average of one
hydrogen bond per molecule.
However, in water there are 2 0-H bonds and 2 unshared pair of electrons per molecules, this
means that each water molecule can form 2 hydrogen bonds, hence the boiling point of water is
higher than HF.
In NH3 molecule, there are 3 N-H bonds but only one unshared pair of electron on nitrogen
atom. This means that there can be an average of only one hydrogen bond per molecule (like
HF), however the electronegativity of fluorine is more than that of nitrogen. Therefore, the
strength of hydrogen bond is more in HF than in NH3, hence the boiling point of HF is more than
NH3.

Density of ice: Ice is less dense than water and it floats on water. Water molecules are joined
together in an extensive 3-dimensional network, in which each oxygen atom is bonded to 4
hydrogen atoms, 2 by hydrogen and 2 by normal covalent bonds in a nearly tetrahedral
configuration. Ice has a highly ordered 3-dimensional hydrogen bonded structure which has got
open spaces, this is responsible for the low density of ice.

Volatility: It is a measurement of how easily the molecules escape from a liquid. A volatile liquid
loses molecules from the surface very easily so it will have a low boiling point.

Effect of branching in the carbon chains on the boiling and melting temperature of alkanes:
Branching of the molecules lower the boiling temperature because the more the branching the
fewer the points of contact between the adjacent molecules. This leads to an overall decrease
in intermolecular force of attraction and hence decrease in B.P.
Melting point depends on packing of molecules in the crystal lattice, branched hydrocarbons
have a more compact packing and hence possess a higher melting point.

TOPIC 3: REDOX, GROUPS 1,2 AND 7

Oxidation – loss of electrons, gain of oxygen, loss of hydrogen.
Reduction – gain of electrons, loss of oxygen, gain of hydrogen.
Redox reaction – a reaction that involves both oxidation and reduction at the same time.
Oxidising agent – a species that oxidises another species by removing one or more electrons;
when an oxidising agent reacts it gains electrons and is being reduced.
Reducing agent – a species that reduces another species by adding one or two electrons; when
a reducing agent reacts it loses electrons and is being oxidised.
Disproportionation reaction – a reaction involving the simultaneous oxidation and reduction of
an element in a single species.
Oxidising number – the charge that an ion has, or the charge that it would have if the species
were fully ionic.

Rules for determining the oxidation number:

 The oxidation number of an uncombined element is zero.
 The sum of the oxidation numbers of all the elements in a neutral compound is zero.
 The sum of the oxidation numbers of all the elements in an ion is equal to the charge on
the ion.
 The more electronegative element in a substance is given a negative oxidation number.
 The oxidation number of fluorine is always – 1.
 The oxidation number of hydrogen is +1, except when combined with a less
electronegative element. Then it becomes –1.
 The oxidation number of oxygen is -2, except in peroxides where it is –1 and when
combined with fluorine when it is +2
 The oxidation number of chlorine is always -1, except in compounds with fluorine and
oxygen where it is positive.

Equations example:
2Na + 2H2O  2NaOH + H2
Oxidation half equation: 2Na  2Na+ + 2e-
Reduction half equation: 2H+ + 2e-  H2
Ionization energy - the energy required to remove one mole of electron from one mole of a
gaseous atom or ion to form one mole of a gaseous positive ion.
*The energy needed for ionisation is used to overcome the electrostatic attraction between the
electron being removed and the protons in the nucleus.
Ionization energy of Groups 1 and 2:
 As the nuclear charge increases, so the force of attraction for electrons being removed
also increases. This means an increase in IE down the group.
 As each quantum shell is added, energy of the outermost electrons increases. This means
a decrease in IE.
 As the number of filled inner shells increases, their force of repulsion on the electron
being removed increases. This means a decrease in IE.
 The combined second and third factors outweighs the effect of first factor, so there is a
decrease in IE down the group.

Group 1 Reactions:
1. When exposed to air, they tarnish as they are oxidised by oxygen in the air.
2. They are soft, can be cut by a knife, softness increases down the group.
3. Stored under oil to prevent the reaction between moisture and air.
4. Reactivity increases down the group.
Reaction with oxygen to form oxide: 4M(s) + O2(g)  2M2O(s)
Reaction with water: 2M(s) + 2H2O(l)  2MOH(aq) + H2(g)
Reaction with chlorine: 2M(s) + Cl2  2MCl(s)

Group 2 Reactions:
Reactivity increases down the group
Reaction with oxygen: when Mg burns in air bright white flame and a white solid (MgO) are
produced. 2M(s) + O2(g)  2MO(s)
Reaction with water: M(s) + 2H2O(l)  M(OH)2(aq) + H2(g)
Reaction with chlorine: combines with chlorine when heated in the gas. M(s) + Cl2(g)  MCl2(aq)
Magnesium and steam: rapidly forms magnesium oxide (white solid) and hydrogen gas in a
vigorous reaction. H2 formed is burned as it leaves the tube to prevent the escape of a highly
flammable gas.

Reaction of the oxides with water: solids react to form colourless solutions.
*BeO doesn’t react with water. MgO reacts slightly.

Solubility of Group 2 hydroxides: The energy released by hydration increases compared to the
energy needed to break the ionic lattice on moving down the group. Therefore, the compounds
become more soluble as we move down the group.

Solubility of Group 2 sulphates: The energy released by hydration decreases compared to the
energy needed to break the ionic lattice on moving down the group, so the compounds become
less soluble as we move down the group.

Testing for CO2: Pass CO2 through the lime water, it turns milky. Lime water is saturated
aqueous solution of calcium hydroxide. CO2(g) + Ca(OH)2(aq)  CaCO3(s) + H2O(l)
By passing excess CO2 gas through lime water mlkiness disappears due to formation of
Ca(HCO3)2 . CaCO3(s) + H2O(l) + CO2(g)  Ca(HCO3)2(aq)
On heating milkiness reappears due to formation of CaCO 3

Milk of Magnesia: Suspension of magnesium hydroxide in water has been sold as an indigestion
remedy called milk of magnesia, which act as an antacid. It neutralizes the stomach acid ,HCl.
Mg(OH)2 + 2HCl  MgCl2 + 2H2O

Reactions of the oxides and hydroxides with acids: salt and water are formed, neutralization
reactions. A white solid reacts to form a colorless solution, exothermic reaction.

Uses of group 2 elements:

Magnesium – used for flares and incendiary bombs. It is also a powerful oxidising agent and is
used as a sacrificial anode to protect steel structures such as ships and bridges from rusting.
Magnesium Oxide – has a high mp and is used as a lining material in furnaces.
Magnesium Hydroxide – used in indigestion remedies and toothpaste to neutralize acid.
Calcium oxide – used in agriculture to reduce the acidity of soil, used in the manufacture of
cement, plaster.
Calcium Hydroxide – used to demonstrate presence of carbon dioxide, used in water treatment,
used for neutralizing acidic soil.
Barium sulphate - is insoluble and opaque to X-rays. When swallowed by patients, subsequent
X-ray examination may show up imperfections in the soft tissue of the digestive system. Barium
compounds are toxic but the insolubility of barium sulphate makes it safe to use in the body.

Testing for Sulphate ions:

Acidify with dil. HNO3 or dil. HCl and then add barium chloride or barium carbonate solution. A
white ppt is formed.
The ionic equation for the reaction is

Thermal stability – a measure of the extent to which a compound decomposes when heated.
Factors affecting thermal stability:
The hight melting temperature

When Group 2 Nitrates and Carbonates are heated they do not melt, instead they decompose.

Thermal stability of Nitrates:

Nitrates of Group 2 decompose by heating to form oxide, NO2 , O2
2Be(NO3)2  2BeO + 4NO2 + O2
Nitrates of Group 1 decompose to form nitrite and O2 only, except Lithium Nitrate.
2NaNO3  2NaNO2 + O2
4LiNO3  2Li2O + 4NO2 + O2
Brown fumes of NO2 indicates greater decomposition.

*Thermal stability of Group 2 nitrates increases down the Group. Group 2 metal ions become
larger down the group but have the same charge, so their charge density is reduced. A metal
ion with high charge density has strong polarizing power. It can therefore polarise the nitrate
ion by attracting them towards themselves. A metal ion with a low charge density has weak
polarising power, meaning nitrate ion is less polarised and therefore more thermally stable.
*Group 2 compounds are less thermally stable than than Group 1 compounds. The greater the
charge on the cation, the greater the distortion and the less stable the nitrate ion becomes.

Thermal stability of carbonates:

Group 2 carbonates decompose to form oxide and CO2
CaCO3  CaO + CO2
Group 1 carbonates do not decompose on heating (except at high temp.) except Lithium
carbonate
Li2CO3  Li2O + CO2

* Thermal stability of Group 2 carbonates increases down the Group. Group 2 metal ions
become larger down the group but have the same charge, so their charge density is reduced. A
metal ion with high charge density has strong polarizing power. It can therefore polarise the
carbonate ion by attracting them towards themselves. A metal ion with a low charge density
has weak polarising power, meaning carbonate ion is less polarised and therefore more
thermally stable.
Thermal stability of oxides:
Thermal stability of oxides of Group 2 decreases down the group, due to increase in size of the
metal ion. Thus, the lattice energy of oxides also decreases down the group. That is the
formation of MgO is more energetically favourable than CaO. The more the lattice energy, the
more the stability.

Flame test:
 Wear safety glasses and a lab coat. Within a fume cupboard, light a Bunsen burner.
 Using a dropper, add a few drops of concentrated hydrochloric acid to the solid and mix
together so that the metal compound begins to dissolve.
 Dip a clean metal wire (platinum or nichrome) or silica rod into the mixture to obtain a
sample of the compound.
 Hold the end of the wire or rod in the flame and observe the colour.

Many cations have no effect on the flame. Sodium has an intense yellow flame which masks the
presence of other cations.
In a flame test the sample is converted to a chloride because chlorides are more volatile than
other salts.

What causes the colours in flame test? Electrons occupy certain discrete energy levels in an
atom or ion. When the electron is promoted from its ground state to a higher energy level the
atoms become excited, when the electrons drop back to the ground state, it emits radiation in
the visible range (400-800nm), the color is due to this emitted radiation. Each element has its
own characteristic energy level (and color).

Test for ammonium ions: Add sodium hydroxide solution and warm the mixture.
NH4+ + OH-  NH3 + H2O warming release of ammonia gas
Ammonia can be recognised by its smell, or damp litmus paper turns blue.
Test 2: HCl reacts with ammonia to form white smoke of ammonia chloride.
NH3 + HCl  NH4Cl
Group 7 elements are known as halogens due to their salt forming character.

They exist as diatomic molecules. So their melting and boiling point depends on the strengths of
the intermolecular forces of attraction between these molecules (London forces). Melting and
Boiling temperature of Group 7 elements increases down the group due to increase in the
strength of intermolecular forces due to increase in electron number and the molecules
become larger.

Equations for change of state:

When Bromine is left at room temp. it gives off brown vapour as its boiling point (59 0C) is not
much higher than room temp. Br2(l)  Br2(g)
When Iodine is warmed, most of it changes directly into a vapour without melting. This change
is called sublimation. I2(s)  I2(g)

Trend in electronegativity: The electronegativity of an atom depends on:

 its nuclear charge – the bigger the nuclear charge, the higher the electronegativity
 the distance between the nucleus and the bonding pair of electrons – the shorter the
distance, the higher the electronegativity
 the shielding effect of electrons in inner energy levels – the fewer energy levels, the
higher the electronegativity.
The electronegativity of the Group 7 elements is the highest of any group in the Periodic Table.
The electronegativity of fluorine is the highest of all elements.
*The electronegativity of Group 7 elements decreases down the group as the radius of each atom
increases due to more shells. This means there is less attraction between the positive nucleus and
the outer electrons as you go down the group.

Trend in reactivity:
Their reactivity decreases down the group as the shielding effect increases meaning that the outer
electron is less attracted to the nucleus. Group 7 elements are very reactive and are strong
oxidizing agents.

Q. Explain why fluorine has the highest electronegativity? Since it has lowest shielding effect
due to only two electrons in the innermost shell. It has a very small distance between the
nucleus and the outer electrons.

Reactions with metals in Groups 1 and 2:

  Reactions are most vigorous between elements at the bottom of Groups 1 and 2, and
elements at the top of Group 7. The most vigorous reaction should be between caesium
(or francium) and fluorine, and the least vigorous between beryllium and iodine (or
astatine).
 The products of these reactions are salts, ionic solids that are usually white.
 All of these reactions involve electron transfer to the halogen, so they are redox reactions
in which the halogen acts as an oxidising agent.
 The oxidation number of the halogen decreases from 0 to – 1, and the oxidation number
of the metal increases from 0 to +1 or +2, depending on the group.

Halogen/Halide displacement reaction:

A more reactive halogen can displace a less reactive halogen from one of its compounds.
These reactions occur in aqueous solution, so any reaction that occurs is indicated by a colour
change. One problem in interpreting colour changes in these reactions is the similarity of some
colours and the variation in colour with concentration. When doing these reactions, it is a good
idea to add an organic solvent (such as cyclohexane) after the reaction, and then shake the tube.
Halogens are more soluble in cyclohexane than in water, so the halogen dissolves in the organic
upper layer, where its colour can more easily be seen.

Chlorine is the most reactive of the three because:

 it is the smallest atom, so the incoming electron gets closer to, and is more attracted by,
the protons in the nucleus.
 it has the smallest number of complete inner energy levels of electrons, so the incoming
electron experiences the least repulsion.

Disproportionation reactions of chlorine:

1) Chlorine with water: Cl2 + H2O  HCl + HClO
0 -1 +1
2) Chlorine with cold alkali: Cl2 + 2NaOH  NaCl + NaClO + H2O
0 -1 +1
3) Chlorine with hot alkali: 3Cl2 + 6NaOH  5NaCl + NaClO3 + 3H2O
0 -1 +5

Redox reactions:
Observations and products:

1) Sodium chloride: NaCl + H2SO4  NaHSO4 + HCl

2) Sodium bromide: NaBr + H2SO4  BrHSO4 + HBr
2HBr + H2SO4  SO2 + H2O + Br2
The ionic equations are
2Br-  Br2 + 2e-
H2SO4 + 2H+ + 2e-  2H2O + SO2
Reddish brown vapours of bromine is produced , In this case Sulfur changes its oxidation
number from +6 to +4 .
3) Sodium Iodide: NaI(s) + H2SO4 (l) → NaHSO4(s) + HI (g)
HI reduces H2SO4 to Sulfur
6HI + H2SO4  4H2O + S + 3I2
The ionic equations are:
2I-  I2 + 2e- (multiply by 3)
H2SO4 + 6H+ + 6e-  4H2O + S
6I- + H2SO4 + 6H+  4H2O + S + 3I2

Testing for halide ions in solution:

The reagent is silver nitrate solution, but first dilute nitric acid is added to prevent the
precipitation of any other silver salt (such as carbonate), then silver nitrate is added.

The general ionic equation for the formation of the precipitate is

Ag(aq)+ + X(aq)-  AgX(s)
You can write a specific equation such as
AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq)

Reactions with water:

Hydrogen halides readily react with water to form acidic solutions, all of which are colourless.

The strength of halogen acid is in the order HI > HBr > HCl > HF
This is because the bond dissociation energy of H-I bond is the least due to the bigger size of
iodine atom. Therefore it will release proton easily and hence it is more acidic. Fluorine and
astatine behaves in a similar way.
Reactions with ammonia:
Hydrogen halides all react with ammonia gas to form salts, all of which are ionic solids.

Making a standard solution of Sulfamic acid:

You need to have an idea of the approximate concentration and volume of the solution to be
made. Typical values are 0.1 mol dm-3 and 250 cm3. The approximate amount can be calculated
by n=cV = 0.1 x 0.25 = 0.025 mol so the approximate mass needed is m=n x M= 0.025 x 97.1=2g
Apparatus:
 Safety glasses and a lab coat
 An accurate balance ( we will assume one reading to 3 d.p.)
 A weighing bottle
 A spatula
 A 250 cm3 beaker
 A 250 cm3 volumetric flask
 A wash bottle containing deionised water (or distilled water)
 A small funnel
 A glass stirring rod
Method:
1. Add between 2.3 and 2.5 g of sulfamic acid to the weighing bottle and weigh accurately.
2. Transfer as much as possible of the acid to a clean beaker and reweigh the weighing
bottle.
3. Add about 100 cm³ of deionised water to the beaker and stir until all of the sulfamic acid
has dissolved.
4. Remove the stirring rod, washing traces of solution from the rod into the beaker using the
wash bottle.
5. Place a funnel in the neck of the volumetric flask and pour the solution from the beaker
into the flask.
6. Rinse the inside of the beaker several times using the wash bottle and transfer the rinsings
to the flask.
7. Add deionised water to the flask and fill up exactly to the graduation mark.
8. Stopper the flask and invert it several times to make a uniform solution.
*When making a standard solution in a volumetric flask, it is important to ensure that the
lowest part of the liquid (the meniscus) is aligned with the graduation mark.
Titration

Titration 1 is not concordant because it is normal practise to do the first titration more quickly
to obtain a rough titre, so the endpoint is more likely to be overshot.
TOPIC 4: KINETICS AND EQUILIBRIUM
Rate of reaction – amount of reactant consumed in unit time or the amount of products
formed in unit time.
Factors affecting rate of reaction:
Concentration – As concentration increases, the rate of reaction increases. As concentration
increases, there are more particles in a given volume. Therefore the frequency of successful
collisions increases which in turn produces an increase in the rate of reaction.
Pressure – For a reaction in gaseous phase, an increase in pressure will cause an increase in the
rate of reaction. As pressure increases, the number of particles per unit volume increases.
Therefore the frequency of successful collisions increases which in turn produces an increase in
the rate of reaction. Changing pressure has almost no effect on the reaction in solids and liquids
phase.
Temperature – As the temperature increases so does the rate of reaction. When the
temperature is raised, the number of particles is unchanged but the average energy of each
particle increases and they move faster. That means more collisions will have activation energy
to result in a reaction. That is the number of successful collisions increases which in turn
produces an increase in the rate of reaction.
Surface area - As surface area increases, the rate of the reaction increases. For a reaction to
happen, the particles of the reactants must be brought into contact with each other. As the surface
area increases, more particles will be in contact with each other and the frequency of successful
collisions increases which in turn produces an increase in the rate of reaction.

Maxwell Boltzman distribution

Effect of temperature: for every 100 rise of temperature, the rate of reaction gets doubled.
Explanation: As the temperature increases, the curve flattens towards the right and greater
proportion of molecules exceeds activation energy. The area under the curve remains the same.
By increasing the temperature, the number of energetically effective collisions increase and
hence the rate of reaction increases.

Effect of a catalyst: Catalyst provides an alternative path which lowers activation energy for the
reaction to occur so the number of successful collisions increases and hence rate of reaction
increases.
Energy profile diagram of a catalysed reaction
A – activation energy of uncatalyzed reaction
B – activation energy of catalysed reaction
X – intermediate

Reversible reaction – a reaction that takes place in both forward and backward directions.
Equilibrium is dynamic in nature, this is because at equilibrium the rate of forward reaction is
equal to the rate of backward reaction.
If a reaction is obtained in a closed system, after sometime the reaction comes to a standstill, at
this point we can say that equilibrium is reached. The reaction doesn’t go to completion. The
position of equilibrium is not fixed for a reaction, but changes as we change the reaction
conditions.

Equilibrium constant: general equation aA + bB  cC + dD

The equilibrium constant is given by

Le chatlier’s principle: states that if we change either temperature, pressure or concentration

of a system at equilibrium, the system will adjust itself in that direction to cancel the effect of
change.

Effect of concentration: If we increase the concentration of any of the reactants, the forward
reaction is favoured, that is, the equilibrium shifts to the right so as to cancel the effect of that
change according to Le Chatlier’s principle. If we increase the concentration of products, the
backward reaction is favoured.
Effect of temperature: Consider for example H2 + I2  2HI H = -x kJ/mol
Here the forward reaction is exothermic, therefore increasing temperature of the system at
equilibrium, the equilibrium shifts to the left (reverse reaction is favoured). To get more HI, we
have to reduce the temperature of a system at equilibrium.

Effect of pressure: On increasing the pressure, the volume occupied by the system will
decrease. By increasing the pressure of a system at equilibrium , the equilibrium will shift to the
side with less number of moles of gases.
Pressure has virtually no effect on the chemistry of solids and liquids.
Effect of adding catalyst: if a catalyst is added to a reaction mixture that is in equilibrium, the
rate of both the forward and the backward reactions will increase. The position of equilibrium
will not be altered. The advantage of adding a catalyst at the beginning of the reaction is that it
will reduce the time required to establish equilibrium.

Haber process of manufacture of ammonia: N2(g) + 3H2(g)  2NH3(g) H = -92 kJ mol-1

Conditions: temperature 4500C , pressure 200 atm, catalyst finely powdered iron
 Since the forward reaction is exothermic, a low temperature could produce a higher yield
of ammonia in the equilibrium mixture. However, a low temperature would reduce the
rate of reaction, so the reaction would take a long time to reach equilibrium, making the
process uneconomic. Therefore, an optimum temperature of 450°C is used.
 Since the forward reaction involves a decrease in the number of moles of gas, a high
pressure could produce the highest yield of ammonia.
 A high pressure also increases the rate at which ammonia is produced (This is because,
by increasing the pressure, the number of particles per unit volume increases, as a result
frequency of successful collisions increases and hence the rate of reaction increases).
 However, high pressure equipments are expensive and difficult to maintain. In practice,
an optimum pressure of 200 atom is used.
Contact process for the manufacture of sulphuric acid:
2SO2 + O2  2SO3 H = -ve
SO2 is made by burning sulfur in dry air , it is then oxidized to SO3, which is dissolved in
concentrated H2SO4 to make oleum, which is then diluted with water to give H2SO4
S + O2  SO2
2SO2 + O2  2SO3
SO3 + H2SO4  H2S2O7 (oleum)
H2S2O7 + H2O  2H2SO4
Since the forward reaction is exothermic, a low temperature would produce the highest yield
of SO3 in the equilibrium mixture. However, a low temperature could reduce the rate of the
reaction, and the reaction would take long time to reach the equilibrium making the process
uneconomic. Therefore, the optimum temperature of 450°C is used.
Since the forward reaction involves a decrease in moles of the gas, high pressure would
produce the highest yield of SO3. High pressure also increases the rate. However, high
pressure equipments are expensive and difficult to maintain. In this reaction, it doesn't
significantly increase the yield of SO3, therefore the reaction is carried out at atmospheric
pressure (1-2 atm)

TOPIC 5: ORGANIC CHEMISTRY, ALCOHOLS, SPECTRA

General formula: CnH(2n+1) – X X - halogen
CnH2n – X2
CnH(2n-1) – X3
CnH(2n-2) – X4

Q. What makes halogenoalkanes more reactive?

Presence of halogen atoms which are more electronegative than carbon makes C-X bond
polar. The electronegativity of halogens decreases from fluorine to iodine, so the polarity of
C-X bond also decreases.
The carbon atom joined to the halogen is always the slightly positive or electron-deficient
part of the molecule, and this what makes halogenoalkanes react as they do. These carbon
atoms attract nucleophiles.
Nucleophile – a species that donates a lone pair of electrons to form a covalent bond with an
electron-deficient atom.