As Chemistry Revision Notes

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Information Technology

ISBN ~-84085-505-3

9 781840 855050

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• .1

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The modern Periodic Table 38

Trends in boiling point 39

Trends in atomic radii 40

Trends in first ionisation energies 41

Oxidation and reduction 42

Using oxidation numbers with equations 43

The s-block elements: Group 1 and Group 2 44

The Group 1 elements 4.5

Contents

Atomic structure

Atoms and isotopes 4

The electronic structure of the atom 5

Orbitals : 6

Electronic. configuration 7

Ionisation energy 8

Progress check '" 10

Atoms, moles and equations

Relative masses 11

Calculating a relative atomic mass 12

The mole and molar mass 13

Moles from solutions 14

Moles from gas volumes 15

Types of chemical formula 16

Balancing equations 17

Reacting quantities 18

Acid-base titrations 19

Progress check 20

Bonding and structure

Chemical bonding 22

Ionic bonding : 23

Ionic charges and the Periodic Table 24

Covalent bonding 25

Shapes of molecules 26

Ionic or covalent? 27

Electronegativity 28

Polar and non-polar molecules 29

Intermolecular forces 30

Hydrogen bonds 31

Bonding and structure in metals 32

Properties of ionic compounds 33

Properties of simple molecular structures 34

Properties of giant molecular structures 35

Summary of properties from structure and bonding 36

Progress check 37

The Periodic Table

2

The Group 2 elements 46

The thermal stability of s-block compounds · 47

The Group 7 elements and their compounds 48

Halides 49

Uses of chlorine 50

lodine-thiosulphate tltratlons 51

Extraction of metals 52

Progress check 53

Chemical energetics

Enthalpy changes 54

Standard enthalpy changes 55

Direct determination of enthalpy changes 56

Bond enthalpy 57

Indirect determination of enthalpy changes 58

Progress check : 60

Rates and equilibrium

Reaction rates 61

The Boltzmann distribution : 62

The effect of a temperature change on reaction rate 63

Homogeneous catalysis 64

Heterogeneous catalysis 65

Chemical equilibrium " 66

The Haber Process for the production of ammonia 68

Acids and bases ; 69

Progress check 70

Organic chemistry

Formulae, alkanes and alkyl groups 71

Functional groups 72

Hydrocarbons and isomers 73

Naming organic compounds 74

Types of bond fission 75

Hydrocarbons from oil 76

Alkanes 77

Alkenes 78

Addition polymerisation of alkenes 80

Alcohols 81

Oxidation of alcohols 82

Further reactions of alcohols " 83

Halogenoalkanes 84

Further reactions of halogenoalkanes 85

Key reaction mechanisms : 86

Progress check 88

Progress check answers 89

The Periodic Table 94

Index 95

AS Chemistry Revision Notes

"

3

Atomic structure

Atoms and isotopes

Sub-atomic particles

• An atom is composed of three sub-atomic particles: protons, neutrons and electrons.

• Protons and neutrons form the nucleus at the centre of the atom with electrons orbiting in shells.

nucleus (protons and neutrons)

electron shells

• Compared with the total volume of an atom, the nucleus is tiny and extremely dense.

• Most of an atom is empty - space between the nucleus and the electron shells.

Properties of protons, neutrons and electrons

particle . relative mass relative charge
proton, p I 1+
neutron, n 1 0
electron, e T/1840 T- All atoms are electrically neutral.

• The charge on a proton is opposite to that of an electron but each charge has the same magnitude.

• The charges balance - an atom must have the same number of protons as electrons.

• The mass of the proton is virtually identical to the mass of a neutron.

• The mass is made up almost entirely from the masses of the protons and neutrons.

Isotopes

Elements exist naturally as a mixture of isotopes.

• Isotopes are atoms of the same element with different masses.

• Isotopes of an element have the same number of protons as electrons.

• Each isotope has a different number of neutrons mass number

. th I (protons + neutrons) -...........-.

III e nuc eus. :A

AX ~z

atomic number

(protons)

The isotopes of carbon

Carbon exists as three isotopes, l:C, l:C, l:C.

isotope atomic mass
number, z. number, A protons neutrons electrons
1"2 6 12 6 6 6
6C
I~C 6 13 6 7 6
6
14C 6 14 6 8 , 6
6 The number of protons in the nucleus identifies the element - all atoms of carbon have 6 protons. The isotopes of an element react in the same way - chemical reactions involve electrons: neutrons make no difference to chemical reactivity.

(

AS Chemistry Revision NoteS

Energy levels or 'shells'

The number of electrons that can occupy the first four energy levels is shown below.

The principal quantum shell, n, is the shell number.

n shell electrons
~1-:-' 1 st snell 2
2 2nd snell 8
3 3ra shell 18
4 4th shell 32 • The number of electrons that can occupy a shell is 2n2.

• Electrons are placed into shells, starting with the lowest energy level.

• Each shell must be full before the next shell starts to fill.

Sub-shells

• There are four different types of sub-shell: s, p, d and f.

• Each type of sub-sbell'"Cari hold a different number of electrons.

sub-shell electrons
s 2
p 6
d 10
f 14 • Each shell is made up of sub-shells.

energy

32e-

n = 4 ---'--'---

n=3

n=2

n=1

. Electronic energy levels are like a ladder and are filled from the bottom up. Notice that the gap between successive energy levels becomes less with increasing energy.

n shell sub-shell total number of electrons
1 1 st shell 1 s 2 :=2
2 2nd shell 2s 2p 2+6 :=8
3 3rd shell 3s 3p 3d 2 + 6 + 10 :=18
4 4th shell 4s 4p 4d 4f 2 + 6 + 10 + 14 := 32
- Shells, sub-shells and energy

1s---

energy

3d--- 3p---

3s---

4f--- 4d ---:---

4p---

4s---

The electrons occupy subshells in order of sub-shell energy levels.

Each successive shell contains a new type of sub-shell. Within a shetl, the sub-shell energies are in the order: s, P, d and f.

Note that toe 4s sub-shell is at a lower energy than the 3d sub-shell; the 4s sub-shell fills before the 3d sub-shell

The sub-shells within a principal quantum shell have different energies.

2p--- 2s---


5

6

Orbitals

• Each sub-shell is made up of orbitals.

• An orbital can hold up to two electrons.

• Each type of sub-shell has different orbitals: s, p, d and f.

sub-shell number of orbitals electrons
s 1 1 x 2 = 2
P 3 3x2;::;6
d 5 5x2=lO
f 7 7x2=14 s-orbitals

• An s-orbital has a spherical shape.

o

p-orbitals

• A p-orbital has a 3-dimensional dumb-bell shape.

• There are three p-orbitals, Px' P, and Pz' at right angles to one another.

Three p-orbitals

x

giving

d~orbitals and f-orbltals

The structures of d and f-orbitals are more complex.

• There are five d-orbitals.

• There are seven f-orbitals,

'Electrons in a box'

allowed

[ll][IT]

not allowed

[ff][TIJ

How do two electrons fit into an orbital?

• Electrons are negatively charged and so they repel one another.

• An electron also has a proper!y called spin.

• Using 'Electrons in a box', each electron is shown as an arrow, indicating its spin: either t or .,I..

• Within an orbital, the electrons must have opposite spins. This helps to counteract the repulsion between their negative charges.

Filling the orbitals

The diagram below shows how electrons occupy orbitals for 5B, 6C, 7N and 80.

boron carbon nitrogen oxygen
~,p I = t I 12p Itltltl2P Itt I tit 12p
energy n=2- lul2S [fI] 2s I Ul2S
n=1-- [fJJ 1s [IJ 1s [f]1s [tl] 1s
1s'2s'2p" 1s'2s'2p' 1s'2s'2p' 1s'2s'2p' The lowest energy-level is occupied first. The 2s sub-shell is filled before the 2p erbltals .. Orbitals at the same energy level are occupied singly before pairing of electrons - this prevents repulsion between paired electrons,


The electronic configuration of an atom is a shorthand method showing how electrons occupy sub-shells.

element orbitals occu~ied electronic configuration
r B 1 s22s22Px1 1 s22s22r>'
I C 1 s22s22E.'2e)!' 1 s22s22r>2
I N 1 s22s22r> '2f? '2r> ' 1 s22s22r>3
I,: :x.)! z
I 0 1 s22s222x22 '2p' 1 s22s22r>4
Py z Filling the sub-shells

The diagram below shows how the sub-shells are filled in an atom of potassium.

• The sub-shells fill in energy level order.

• Notice that the 4s sub-shell has a lower energy level than the 3d sub-shell - the 4s sub-shell fills before the 3d sub-shell.

4f---- 4d----

4p----

3d;;:;::;:;:::;::;::~4Sm 3p IH·lt +It +1

3s [fJ]

2p It +It +It +1 2s [ll]

Potassium

1s Illl

The 19 electrons of K

19 electrons

IJ~\~

1 s22s22p63s23p64s'

\\'tll

sub-shells

energy

The 4s sub-shell has a lower energy than the 3d sub-shell.

The 4s sub-shell is occupied before the 3d sub-shell.

Sub-shells and the Periodic Table

The Periodic Table is structured in blocks of 2, 6, 10 and 14, linked. to sub-shells. The order of sub-shell filling can be seen by dividing the Periodic Table into blocks.

ls 15
Is-block .p-block
25 2R
35 a-block 3p
45 3a . 4R'
55 4d JL 5p
65 5d JI 6e
75
t-bkxk

4f

5f

Electronic configurations can be simplified in terms of the previous noble gas. The electronic configurations for the elements in Group 1 are shown below:

Li: 1s22s' or [Hel2s'

Na: ls22s22p63s' or [Ne]3s,

K: 1 s22s22p63s23p64s' or [ArJ4s'


7

Ionisation energy

Ionisation energy measures the ease with which an atom loses electrons in the formation of positive ions.

The first ionisation energy of an element is the energy required to remove

1 electron from each atom in 1 mole of gaseous atoms to form ] mole of gaseous 1 + ions.

E.g. Na(g) -- Na+(g) + e

1st ionisation energy == +496 kJ marl

Factors affecting .ionisation energy

• Electrons are held in their shells by attraction from the nucleus.

• The first electron lost will be from the highest occupied energy level - this

electron experiences least attraction from the nucleus.

Three factors affecting the size of this attraction are shown below. 1 . Atomic radius

• The greater the distance between the nucleus and the outer electrons, the less the attractive force.

• Attraction falls off rapidly with increasing distance and so this factor is very important and has a big effect.

2 Nuclear charge

• The greater the number of protons in the nucleus the greater the attractive force on the outer electrons.

3 Electron shielding or screening

• The outer shell electrons are repelled by any inner shells between the electrons and the nucleus.

• This repelling effect, called electron shielding or screening, reduces the overall

attractive force experienced by the outer electrons. .

->

Evidence for shells

Success.ive ionisation energy

Successive ionisation energies provide evidence for different energy levels. An element has as many ionisation energies as there are electrons.

The second ionisation energy of an element is the energy required to remove 1 electron from each atom in 1 mole of gaseous 1+ ions to form 1 mole of gaseous 2+ ions.

E.g. Na+(g) -- Naz+(g) + e 2nd ionisation energy = +4563 kJ mol'

Sodium, with 11 electrons, has 11 successive ionisation energies:

. /' These 2 electrons are in the 1st

.:' shell (n = 1), Closest to the nucleus r These electrons experience very strong attractive forces from the nucleus.

ionisation energy IkJ mol?

~

These B electrons are in the 2nd shell (n = 2).

These electrons experience reasonably strong attractive forces from the nucleus.

I . I

Thist electron is in the 3rd shell (n = 3), furthest from the nucleus.

Th is electron experiences --------

comparatively weak attractive

forces from the nucleus,

o 2 3 4 5 6 7 8 9 10 11

ionisation number


Evidence for sub-shells

The variation in first ionisation energies across a period in the Periodic Table provides evidence for the existence of sub-shells.

Across Period 2, the first ionisation energy graph shows three sections:

• a rise from lithium to beryllium

Ne

first ionisation energy

• a fall to boron followed by a rise to nitrogen

• a fall to oxygen followed by a rise to neon.

Be

filiingOf2~ sub-shell

li

atomic number

Comparing beryllium and boron

The fall in 1st ionisation energy from beryllium to boron marks the start of filling the 2p sub-shell which is at a higher energy than the 2s sub-shell.

energy ~berylliUm

I 2p

I n-' - H 2s

T' i5::J,p

I n-'-~2S

Beryllium versus boron: 2p sub-shell has a higher energy level than the 2s sub-shell.

• Beryllium's outermost electron is in the 2s sub-shell.

• Boron's outermost electron is in the 2p sub-shell.

• Boron's outermost electron is easier to remove because the 2p sub-shell has a higher energy level than the 2s sub-shell.

Comparing nitrogen and oxygen

The fall in 1st ionisation energy from oxygen to nitrogen marks the start of electron pairing in the p-orbitals of the 2p sub-shell.

nitrogen

elg:=2 _----.:J-f1t It 12p

I 'IDl',

Nitrogen versus oxygen: electron pairing starts.

• Both nitrogen and oxygen have their outer electrons in the same 2p sub-shell with the same energy level.

• Oxygen has one 2p orbital with an electron pair - nitrogen, with one electron in each 2p orbital, has unpaired 2p electrons only.

• Because of electron repulsion, it is easier to remove one of oxygen's paired 2p electrons.

x

Nitrogen

• 2p sub-shell half-full

• 1 electron in each 2p orbital

• parallel spins at right angles

Oxygen

• 2p electrons start to pair

• paired electrons repel

x


9

'Progress check

1 How many protons, neutrons and electrons are in the following isotopes?

(a) ~Li (b) ~~Na (c) ';F (d) ~:AI (e) ~!Fe

2 Write the full electronic configuration in terms of sub-shells for: (a) C

(b) AI

(c) Ca

(d) Fe

(e) Br

Ans~~~~' ~.n page 89 .

. ." . "-~; . . ~

10


Atoms, moles and equations

Chemists use relative masses to compare the atomic masses of different elements. The carbon-12 isotope is chosen as the international standard for the measurement of atomic mass.

• The mass of an atom of carbon-12 is exactly 12 atomic mass units (amu).

• The mass of one-twelfth of an atom of carbon-12 is exactly 1 amu.

Relative isotopic mass

All atoms in a pure isotope have the same atomic structure and the same mass.

Relative isotopic mass is the mass of an atom of an isotope compared with one-twelfth the mass of an atom of carbon-12.

In most chemistry work, it is reasonable to:

• neglect the tiny contribution to atomic mass from electrons

• take both the mass of a proton and a neutron as 1 amu.

Relative isotopic mass is then simplr the mass number of the isotope, e.g. relative isotopic mass: 160: 16; 3Na: 23.

Relative atomic mass

Most elements consist of a mixture of isotopes, each with a different mass number.

Relative atomic mass, AI"' is the weighted average mass of an atom of an element compared with one-twelfth the mass of an atom of carbon-12.

!Relative molecular mass

Many compounds, e.g. H20, CO2, are made up of simple molecules.

Relative molecular mass, M" is the weighted average mass of a molecule of a compound compared with one-twelfth the mass of an atom of carbon-12.

Add together the relative atomic masses of each atom in a molecule. E.g. C12: Mr = 35.5 x 2 = 71; H20: Mr = 1.0 x 2 + 16.0 = 18.0

Relative formula mass

For compounds with giant structures, e.g. ionic lattices and giant molecules, relative molecular mass is often used but a better term is relative formula mass.

Relative formula mass is the weighted average mass of the formula unit of a compound compared with ope-twelfth the mass of an atom of carbon-12.

Add together the relative atomic masses of each atom in the formula.

E.g. CaBrz: relative formula mass = 40.1 + 79.9 x 2 = 199.9

Nal04: relative formula mass = 23.0 x 3 + 31.0 + 16.0 x 4 = 164.0

Note that a relative mass has no units. It is simply a ratio of masses and any mass units will cancel.


11

12

Calculating a relative atomic mass

Measuring relative atomic masses

A relative atomic mass is measured using a mass spectrometer.

• A sample of the element is placed into the mass spectrometer.

• The sample is bombarded with electrons forming positive ions.

• The positive ions are accelerated using an electric field.

• The positive ions are deflected using a magnetic field.

• Ions of lighter isotopes are deflected more than ions of heavier isotopes. This separates different isotopes.

• The ions. are detected to produce a mass spectrum. You can follow the stages in the diagram below.

Magnet

Deflection from magnetic fie.ld

Electron bombardment causes ionisation

Accelerating electric field

Detection of ions

Relative atomic mass from a mass spectrum

To work out the relative atomic mass of an element we must find the weighted average mass of the isotopes present from:

• the percentage abundances of the isotopes

• the relative isotopic masses of the isotopes.

Mass spectrum of a copper sample

:'0

relative percentage
ion isotQpjc mass abundance
63CU+ 63 70%
6·5C~t 65 30% percentage abundance

30

I I I I III I I I I I I I I

60 6JD 70

relative mass

From the mass. spectrum, the copper sample consists of 70% 63CU and 30% 65CU.

The relative atomic mass of the copper {ooo x 63 + 13000 x 65 = 63.6

It is easy to work out a relative atomic mass,

e .. g. chlorine eonslsts of 75% 35C1 and 25% 37CI.

The relative atomic mass of chlorine = 17~0 x 35

+- ~ x 37 = 35.5 100


Amount of substance

Chemists use a quantity called amount of substance for counting atoms. Amount of substance is:

• given the symbol n

• measured using a unit called the mole (abbreviated as moiy.

A mole is the amount of substance that contains as many single particles as there are atoms in exactly 12 g of the carbon-12 isotope.

• The number of atoms per mole of carbon-12 is called the Avogadro constant; L.

• L = 602 000 000 000 000 000 000 000 or 6.02 x 1023 mol".

Counting and weighing atoms

Atoms are weighed out using relative masses.

element

H C 0

1 atom

relative mass

1 12 16

6.02 x 1023 (1 mol) of atoms actual mass

19 12g 16g

The mass of 1 mole of atoms of an element is equal to the relative atomic mass in gramrnes.

Molar mass, M

Molar mass, M, is the mass of one mole of a substance. The units of molar mass. are g mol'.

For elements, the molar mass is simply the relative atomic mass in g mol-l

• Molar mass of Mg = 24.3 g mol".

• This simply means that 1 mole of Mg atoms has a mass of 24.3 g.

For compounds, add together the relative atomic masses of each atom in the formula.

• Molar mass ofCOz = 12 + (16 x 2) = 44 g marl.

• 1 mole of CO2 has a mass of 44 g.

Amount of substance n, mass and molar mass are linked: mass (in g)

n

molar mass

In 24 g of C, amount ofC = mass = 24 = 2 mol

. molar mass 12

In 11 g of CO2! amount oreOz mass 11 == 0.25 mol

molar mass 44

Always quote the formula to which the amount of substance refers.

• '1 mole of oxygen' could refer to oxygen atoms, 0, or to oxygen molecules, 02'

• 1 mole of ° or 1 mole of 02 is unambiguous.


13

Molar concentrations

The molar concentration or molarity of a solution is the amount of solute, in mol, dissolved in 1 drn" (1000 crrr') of solution.

A solution with a concentration of 2 mol dm"

• has 2 moles of solute in 1 dm" of solution

• has a molarity of 2 M

• is a 2 molar solution.

If the volume of the solution is in drrr':

n = c x V (in dm'')

n = amount of substance (in mol)

c = concentration of solute, in mol dm? V = volume of solution, in drn"

For smaller volumes of solutions, it is more convenient to measure volumes in em:' and the expression becomes:

V (in em")

n = c X --':-::--:::-0:----'-

1000

Example

What is the amount of NaCl (in mol) in 25.0 em" of an aqueous solution of concentration 2.00 mol dm"?

V 25

amount, n, of NaCI = c x 1000 = 2.00 x 1000 = 0.0500 mol.

Standard solutions

Chemists often need to prepare standard solutions with an exact concentration. Using an understanding of the mole, the mass required to prepare such a solution can easily be worked out.

Example

Find the mass of sodium carbonate NazC03 required to prepare 250 em" of a 0.100 mol drn " solution.

Find the amount of Na2Ca 3 (in mol) required in solution:

V 250

amount, n, of NazCa3 = c x 1000 = 0.100 x 1000 = 0.0250 moL

Convert moles to gtammes

n = mass

rnolar mass

:. mass = n x molar mass

molar mass of NazC03 = 23.0 x 2 + 12.0 + 16.0 x 3 = 106.0 g mol"

:. mass of NazCa3 required = 0.0250 x 106.0 = 2.65 g.

Concentrations are sometimes measured in g dm'". NazCa3 has a molar concentration of 0.100 mol dm" :. mass concentration of NazCa3 = 10.6 g drrr-'.

14


Molarity refers to the concentration in mol drn".

Thus 2 mol drn? and 2 M mean the same: 2 moles of solute in 1 drrr' of solution.

For a gas, the amount of gas molecules (in mol) is most conveniently obtained by measuring the gas volume.

Provided that the pressure and temperature are the same, equal volumes of gases contain the same number of molecules.

It does not matter which gas is being measured - by measuring the volume, we are indirectly also counting the number of molecules.

At room temperature and pressure (r.t.p.), 298K (25°C) and 100 kPa,

1 mol of a gas molecules has a volume of approximately 24 dm3 = 24 000 cm3•

At r.t.p., if the volume V of the gas is in dm ': n = V (in dm3) 24

At r.t.p., if the volume V of the gas is in em:': n = V (in cm3) 24000

How many moles of gas molecules are in 480 em" of a gas at r.t.p.?

n = V (in cm3) 480 = 0.0200 mol of gas molecules

24 000 24 000 .

The Ideal Gas Equation

• Use the Ideal Gas Equation to find the amount of gas molecules n in a volume V at any temperature T and pressure p.

The Ideal Gas Equation: p V = nRT

P = pressure, in Pa V = volume, in m3 T == temperature, in K

n = amount of gas molecules, in mol R = the ideal gas constant = 8.31 J 1("1 mol"

A 0.215 g sample of a volatile liquid, X, produces 77.5 ern" of gas at 100°C and 100 kPa. Calculate the relative molecular mass of X

Convert values: 77.5 crrr' 100°C 100 kPa

= 77.5 X 10-6 ill3 = 100 + 273 K

= 100 X 103 Pa

= 7.75 x 10-5 rrr' = 373 K

= 1.00 x io' Pa

Use the ideal gas equation:

PV=nRT ·.n= pV . RT

.', ri == 1.00 x 105 x 7.75 x 10-5 = 0.00250 mol of X 8.31 x 373

Find the molar mass

n = mass ... molar mass = mass 0.215 = 86.0 g marl

molar mass n 0.00250


., Relative molecular mass Mr = 86.0 (no units)

Before us.ing pV=nRT, you must remember to convert any values to Pal K and m3•

P kPa to Pa x 1 03

V ern" to m3 x 10-6 dm' to m3 x 10-3

T °C to K +273

15

Molecular and empirical formulae

A molecular formula represents the actual number of atoms of each element in a molecule of a compound.

A molecule of ethane contains 2 carbon atoms and 6 hydrogen atoms. The molecular formula of ethane is CZH6

An empirical formula represents the simplest, whole-number ratio of atoms of each element in a compound.

A molecule of ethane CZH6 contains 2 carbon atoms and 6 hydrogen atoms. Ethane has 1 carbon atom for each 3 hydrogen atoms.

The empirical formula of ethane is CHr

Formula determination

A formula can be calculated from experimental results using the Mole Concept.

Example 1

Find the empirical formula of a compound formed when 6.75 g of aluminium reacts with 26.63 g of chlorine. [A,: AI, 27.0; CI, 35.5.]

Find the molar ratio of atoms: AI CI

=

6.75 27.0 0.25

1

26.63 35.5 0.75 3

Divide by smallest number (0.2S):

:. empirical formula = AICl3

Example 2

Find the molecular formula of a compound containing carbon, hydrogen and oxygen only, with the composition by mass of carbon: 40.0%; hydrogen: 6.7%. [M, = 180. A,: H, 1.00; C, 12.0; 0, 16.0.]

Percentage of oxygen in compound = 100 - (40.0 + 6.7) = 53.3% 100.0 g of the compound contains 40.0 g C, 6.7 g Hand 53.3 g O.

Find the molar ratio of atoms: C H 0

=

40.0 12.0 3.33

1

53.3 16.0 3.33

1

6.7 1.00 6.7

2

Divide by smallest number (3.33):

:. empirical formula = CHzO

Relate to molecular mass:

Each CHzO unit has a relative mass of 12 + (1 x 2) + 16 = 30 Mr of the compound is 180 containing 180/30 = 6 CHP units ... molecular formula is C6H1206

To convert mass to moles: amount in mol

mass (in g) molar mass

16


Write down an equati.on with formulae

The formula of each substance shows the chemicals involved in the reaction. State symbols can be added to show the physical states of each species under the conditions of the reaction.

The qualitative equation for the reaction of hydrogen with oxygen is shown below.

hydrogen + oxygen -----.. water

Hz(g) + 02(g) -----.. Hz0(l)

Check on balancing

In this equation:

hydrogen is balanced, oxygen is not balanced.

H2(g) -+ 0z(g) -- Hp(l)

hydrogen 2 2./

oxygen

2

1

x

The equation must be balanced to give the same number ~f particles of each element on each side of the equation.

Balancing an equation often takes several stages

• Oxygen can be balanced by placing a '2' in front of H20.

• However, this unbalances hydrogen:

Hz(g) + °2(g) hydrogen 2

--

oxygen

2

2

• Hydrogen can be re-balanced by placing a '2' in front of H2•

• The equation is now balanced. 2 Hz(g) + 0z(g)

hydrogen 4

oxygen 2

2

./ ./

Special points

In a formula, a subscript applies only to the symbol immediately before: e.g. NOz comprises 1 Nand 2 0.

When balancing an equation:

• you must not change any formula

• you can only add a balancing number in front of a formula.

The balancing number multiplies everything in the formula by the balancing number:

• 2 AIC13 means AI: 2 x 1 == 2; Cl: 2 x 3== 6.

• 3 Na2S04 means Na: 3 x 2 '" 6; S: 3 x 1 '" 3; 0: 3 x 4 '" 12.

With brackets, the subscript applies to everything in the preceding bracket: • Ca(N03)z means Ca: 1; N: (1 x 2) '" 2; 0: (3 x 2) '" 6.


1i 7

Reacting quantities

The balancing numbers give the ratio of the amount of each substance, in moL Using the example on p.1?:

equation moles

2 Hz(g) +

2 mol

2 HzD(l) 2 mol

Chemists use this information to find:

• the reacting quantities required to prepare a particular quantity of a product

• the quantities of products formed by reacting particular quantities of reactants. By working out the reacting quantities from a balanced chemical equation, quantities can be adjusted to take into account the required scale of preparation.

Example 1

Calculate the masses of nitrogen and oxygen required to form 3 g of nitrogen monoxide, NO [A,: N, 14; 0,16].

equation N2(g)

moles _ 1 mol +

reacting masses (14 x 2) g +

28 g 1.4 g

+

°2(g)

1 mol (16 x 2) g 32 g 1.6g

--

2 NO(g) 2 mol

2 (14 + 16) g 60 g

3g

--

+

for 3 g NO(g), + 20:

+

--

:. 1.4 g of Nz(g) react with 1.6 g of 02(g) to form 3 g NO(g). Example 2

Calculate the volume of oxygen, at r.t.p., formed by the decomposition of an aqueous solution containing 5 g of hydrogen peroxide, HzOz' (Ar: H, 1; 0, 16.]

equation 2 H202(aq) -- 2 H20(l) + °2 (g)
moles 2 mol ----.. 2 mol + 1 mol
reacting quantities 2 [(1 x 2) + (16 x 2)] g -- 24dm3
68 g -- 24dm3
for 1 g HZ02 + 68, 19 -- ~dm3
68 Sg

:. S g of HZ02 decomposes to form 1.8 dm'' of 02(g)

Reacting molar masses from an equation: 4 AI(s) + 3 Dig) -- 2 AIP3(s)

• 4 Ales) means: 4 x 27 = 108 g of AI(s)

• 3 02(g) means: 3 x (16 x 2) = 96 g of Dig)

• 2 AIP3(s) means: 2 x [ (27 x 2) + (16 x 3)] = 204 g AIP3(s).

For gases, molar volumes at r.t.p. are often used:

• 3 0ig) means: 3 x 24 = 72 drn' of Dig).

18


An acid-base titration relies on five pieces of information, one of which is unknown:

• the balanced equation

• the concentration c1 and reacting volume VI of the acid

• the concentration Cz and reacting volume Vz of the base.

Acid-base titrations are usually used to find the concentration of the acid or base.

• The acid is added from the burette to the alkali.

• An indicator shows the 'end-point' when the alkali has just reacted with the acid.

\ ~

Example

In a titration, 25.0 crrr' of 0.100 mol dm' sodium hydroxide NaOH(aq) reacted exactly with lOA em" of sulphuric acid, H2S04(aq). Find the concentration of the sulphuric acid.

To solve the problem, we use the following pieces of information: • the balanced equation

2NaOH{aq) + H2S04(aq) -- NaZS04(aq) + 2HP(l)

• the concentration c1 and reacting volume VI of NaOH(aq)

• the concentration Cz and reacting volume Vz of HZS04(aq).

From the titration results, the amount of NaOH (in moles) can be calculated: amount of NaOH, in mol = ex 1cYoO = 0.100 x ~go~ = 0.00250 mol

From the equation, the amount ofH}04 (in moles) can be determined:

2 NaOH (aq) + HZS04(aq) -- NazSOiaq) + 2HP(l)

2 mol 1 mol (balancing numbers)

:. 0 . .00250 mol NaOH reacts with 0.00125 mol H2S04 amount of H2S04! in mol that reacted = 0.00125 mol

The concentration in mol dm" ofH}04 can be calculated by scaling to 1000 em': 10.4 em" HzSOiaq) contains 0.00125 mol HZS04

1 crrr' HzS04(aq) contains 0.Og125 mol HZS04

1 .4

1 drrr' (1000 ern") H SO (aq) contains 0.00125 x 1000 = 0.120 mol H2S04

z 4 10.4

:. concentration of HZS04(aq) is 0.120 mol drn"

Key points for titration calculations:

• solution volumes to moles: amount in mol, n = c x V (~~~~3)

• reacting molar quantities from balanced equation

• scaling to give the molar concentration per drn",


19

1 Calculate the relative atomic mass, A" of the following elements from their isotopic abundances.

(a) Gallium containing 60% 69Ga and 40% 71Ga.

(b) Silicon containing 92.18% 2BSi, 4.71 % 29Si and 3.11 % 30Si.

2 Use A, values from the Periodic Table to calculate the relative formula mass of: (a) CO2

(b) NH3

(c) Fep3

(d) C6H,P6

(e) Pb(N03)2

3 (a) Find the amount of each substance (in mol) in the following: (i) 124 9 P

(ii) 64 gO

(iii) 64 9 02

(iv) 109 CaC03 (v) 3.04 9 Crp3

(b) Find the mass of each substance (in g) in the following: (i) 0.1 mol Na

(ii) 2.5 mol N02

(iii) 0.3 mol Na2S04

(iv) 0.05 mol H2S04

(v) 0.025 mol A92C03

4 (a) Find the amount of each substance, in mol, in: (i) 250 ern" of a 1.00 mol dm" solution

(ii) 10 crrr' of a 2.0 mol drn' solution

(b) Find the concentration, in mol dm', for:

(i) 4 mol in 2 dm' of solution

(li) 0.0100 mol in 100 ern' of solution.

(c) Find the concentration, in 9 dm'", for: (i) 2 mol of NaOH in 4 dm' of solution

(ii) 0.500 mol of HN03 in 200 ern" of solution.

5 (a) Find the volume, at room temperature and pressure (r.t.p.) of: (i) 44 9 CO2(g)

(ii) 7 9 NzCg)

(iii) 5.1 9 NH3(g)

(b) Find the mass, at r.t.p. of: (i) 1.2 dm" 02

(li) 720 ern" COig) (iii) 48 ern" CH/g)

20


6 Find the formula of the following:

(a) sodium oxide (2.3 9 of sodium reacts to form 3.1 g of sodium oxide) (b) iron oxide (11.16 9 of iron reacts to form 15.96 9 of iron oxide).

7 Using the following % compositions by mass, find the empirical formula for: (a) a compound of sulphur and oxygen [5, 40.0%; 0, 60.0%]

- \ .

(b) a compound of iron, sulphur and oxygen. [Fe, 36.8%; 5, 21.1 %; 0, 42.1 %]

8 2.8 g of a compound of carbon and hydrogen formed when 2.4 9 of carbon combined with hydrogen. [M,:56]. What is the empirical and molecular formula of the compound formed?

9 Balance the following equations. (a) U(s) + 02(g) - UP(s)

(b) CH/g) + O/g) - COig) + Hp(l) (c) AI(s) + HCI(aq) - AICl3(aq) + H/g)

10 For the reaction: 5(s) + 02(g) - 502 (g)

(a) How many moles of 5 and 02 react to form 0.5 mole of 50/ (b) What mass of S02 is formed by reacting 64.2 9 of S with 0/

(c) What volume of S02 forms when 0.963 9 of S reacts with 02 at r.t.p.?

11 Balance the equation: Mg(s) + 0ig) - MgO(s) (a) What mass of MgO forms by burning 8.1 9 of Mg?

(b) What volume of 02 at r.t.p. will react with this mass of Mg?

(c) What masses of Mg and 02 are needed to prepare 1 9 of MgO?

12 (a) 25.0 crrr' of 0.500 mol drrr? NaOH(aq) react with 23.2 ern! of HN03(aq).

HN03(aq) + NaOH(aq) - NaN03(aq) + HP(I) Find the concentration of the nitric acid, HN03•

(b) 25.0 em" of 1.00 mol dm" KOH(aq) react exactly with 26.6 cm ' of H2SO/aq).

H2SO/aq) + 2KOH(aq) - K1S04(aq) + 2HP(I) Find the concentration of the sulphuric acid, H2S04,


21

Bonding and structure

The Octet Rule

Under normal conditions:

• the only elements that exist as single atoms are the Noble Gases in Group 0 of the Periodic Table.

The Noble Gases get their name from their unreactivity.

In the atoms of a noble gas:

• all electrons are paired

• the bonding shells are full.

He atom 1 S2

Ne atom 1s22s22p6

This arrangement of electrons is particularly stable - often referred to as a stable 'octet' (as in neon and argon).

Apart from the Noble Gases, atoms are bonded together.

• Atoms of other elements bond together: oxygen and nitrogen exists as 02 and N2.

• Atoms of different elements bond together in compounds: e.g. COz' CO and

NaCl.

In all these examples, electrons have been shared, transferred or rearranged in such a way that the atoms of the elements have acquired a noble gas electron structure. If this creates an outer shell of 8 electrons (as in all these cases), the 'Octet Rule' is obeyed.

This tendency to acquire a noble gas electron structure is often referred to as the 'Octet Rule'.

Types· of bonding

Chemical bonds are classified into three main types: ionic, covalent and metallic.

• Ionic bonding occurs between the atoms of a metal and a non-metal; e.g. NaCl, MgO, Fep3'

• Covalent bonding occurs between the atoms of non-metals; e.g. 0z' Hz, H20, diamond and graphite.

• Metallic bonding occurs between the atoms of metals;

e.g. all metals such as iron, zinc, aluminium, etc.; alloys as in brass (copper and zinc), bronze (copper and tin).

Always decide the type of bonding before:

• drawing a 'dot-and-cross' diagram

• predicting how a compound reacts

• predicting the properties of a compound.

Many mistakes are made in chemistry by confusing the type of bonding.

Covalent and ionic compounds are bonded differently and they behave differently. You cannot apply 'ionic bonding ideas' to a compound that is covalent.

22


, Ionic bonding

~.

Ionic bonds

• Ionic bonds are present in a compound of a metal and a non-metal.

• An ionic bond is formed when electrons are transferred from a metal atom to a non-metal atom forming oppositely-charged ions.

An ionic bond is the electrical attraction between oppositely charged ions.

Example: sodium chloride, NaCI

Sodium chloride, NaCl is formed by transfer of one electron from a sodium atom ([Ne]3s1) to a chlorine atom ([Ne]3s23p5) with the formation of ions:

• A sodium atom has lost an electron to acquire the electron structure of neon:

Na ~ Na+ + e

[N e]3s 1 ----oo[N e] + e-

• A chlorine atom has gained an electron to acquire the electron structure of argon:

Cl + e- ---.. cr

[Ne]3s23ps + e ----00 [Ar]

Example: magnesium chloride, MgCI2

A magnesium atom ([Ne]3s2) has two electrons in its outer shell. One electron is transferred to each of two chlorine atoms ([Ne]3s23p5) forming ions.

ionic bond forms: attraction between ions

------..~[0r [Mgt [0r

M 2+.

CI.- ion g Ion CI- ion

transfer of 2 electrons

Mg atom

CI atom

CI atom

Giant ionic lattices

In the solid state each ion is surrounded by oppositely-charged ions, forming a giant ionic lattice.

• Although it is convenient to look at ionic bonding between two ions only, each ion is able to attract oppositely charged ions in all directions.

• This results in a giant ionic lattice structure comprising hundreds of thousands of ions (depending upon the size of the crystal).

Part of the sodium chloride lattice

CI

• This arrangement is characteristic of all ionic cojllPounds.

• Each Na" ion surrounds 6 cr ions

• • Each Cl" ion surrounds 6 Na+ ions

For showinq chemical bonding, 'dot-and-cross' diagrams often only show the outer shell.

In an ionic compound, the ions often have stable noble gas electron structures with full outer electron shells.


23

An ionic charge can be predicted from an element's position in the Periodic Table. The diagram below shows elements in Periods 2 and 3 of the Periodic Table.

grouR. 1 2 3 4 5 6 7 0
number of outer shell electrons 1 2 3 4 5 6 7 8
element li Be B C N 0 F Nel
ion li+ Nl" 02 F
element Na Mg AI Si P S CI Ar
ion Na+ Mg~+ A13+ p3= 52 CI-
""'-'" • Metals in Groups 1-3 lose sufficient electrons from their atoms to form ions with the electronic configuration of the previous noble gas.

• Non-metals in Groups 5-7 gain sufficient electrons to their atoms to form ions with the electronic configuration of the next noble gas.

• Be, B, C and Si do not normally form ionic compounds because of the large amount of energy required to transfer electrons forming ions.

Groups of covalent-bonded atoms can also lose or gain electrons to give ions:

1+ 1- 2- 3-
ammonium NH + hydroxide OW carbonate CO~z ~hosJ:lhate PO 3
4 ~..4
nitrate N03- sulphate SO 2
4
nitrite N02- sulphite SO 2
3
hydrogencarbonate HC03 Predicting ionic formulae

Although an ionic compound comprises charged ions, its overall charge is zero.

In an ionic compound:

total number of positive charges from positive ions

=

total number of negative charges from negative ions

Working out an ionic formula from ionic charges

calcium chloride: ion charge aluminium sulphate: ion charge
CaL+ 2+ AIH 3+
AI 3 .. 3+
equalise charges: equalise charges: SO 2-
CI- 1- 4 2-
cr 1- SO 2- 2-
4
SO 2- 2-
4
total charge must be zero: 0 total charge must De zero: 0
formula: CaCI2 formula: AI2(S04)3 Ionic charge can be predicted from an element's position in the Periodic Table. Note that Be, B, C and 5 do not usually form ions.

24


• Covalent bonds are present in a compound of two non-metals.

• A covalent compound comprises molecules.

• A molecule is the smallest part of a covalent compound that can take part in a reaction.

A covalent bond is formed when electrons are shared rather than transferred.

A covalent bond is a shared pair of electrons.

Single covalent bonds

. The covalent bond in a hydrogen molecule Hz forms when two hydrogen atoms (lsI) bond together, each contributing 1 electron to the bond:

Multiple covalent bonds

Atoms can share more than one pair of electrons to form a multiple bond

• Sharing of two pairs of electrons forms a double

bond, e.g. 0z' written as 0;:0. ±J

• Sharing of three pairs of electrons forms a triple ( 0 .~ 0 . ~

bond, e.g. N2~ written as N=N. ~

00

A covalent bond in which one pair of electrons is shared is known as a single

13' 13' bond, e.g. H2, written as H-H

In forming the covalent bond, each hydrogen atom in the Hz molecule has:

• control of 2 electrons - one of its own and the second from the other atom;

• the electronic configuration of the noble gas helium.

Unlike an ionic bond, a covalent bond is directional and acts solely between the two atoms involved in the bond - hydrogen above exists simply as Hz molecules.

Notice that each atom contributes one electron to the covalent bond.

CI2

H20

NH,

CH.

The ammonium ion, NH4+: .

• has three covalent bonds and one dative ~~. N • H

covalent bond

• is formed when ammonia NH3 bonds with H+. H

NH3

+
H+ cq~)

NH/
[.+.J 0,

N,

Dative covalent bonds

A dative covalent or coordinate bond is one in which one of the atoms supplies both the shared electrons to the covalent bond.

In a dative covalent bond the involvement of the electron pair is often shown as an arrow. Once NH/ has formed, aU 4 bonds are equivalent - you (annat tell which was formed by a dative covalent bond.


25

Electron-pair repulsion theory states that the shape of a molecule depends upon the number of electron pairs surrounding the central atom.

• Electron pairs repel one another as far apart as possible.

Molecules with bonded pairs

You can predict the shape of a molecule by examining its 'dot-and-cross' diagram. The repulsion between electron pairs gives the three-dimensional shape of the molecule.

molecule

dot- and-cross diagram

electron pairs around central atom

shape and bond angle

name of shape

5

6

2

3

4

F H F
b12O' b1OB5' CI F ~.
180' CI~")~~o' <. ..,F
CI~CI .s:
C . F-""I'F
/, H/j'\ l ..... cl
F F H CI F
linear trigonal planar tetrahedral trigonal bipyramid octahedral Molecul.es with lone pairs

A lone pair has a larger repulsive effect than a bonded pair of electrons. The relative magnitudes of electron-pair repulsions are: lone-pair/lone-pair > bonded-pair/lone-pair > bonded-pair/bonded-pair.

Each lone pair reduces the bond angle by about 2.50

molecule eM.
, dot-and-cross' +
diagram
number of
lone pairs 0
H
shape and I
bond angle c
H(OH
H 109.5'
name of shape tetrahedral Molecules with double bonds

In molecules containing multiple bonds, each double bond is treated in the same way as a bonded pair. Each double bond is treated as a 'bonding region'.

molecule

26

'dot-and-cross' diagram

2

pyramidal

non-linear

number of bonding regions

2

shape and bond angle

name of shape

linear


An ionic bond with 100% ionic character would require the complete transfer of an electron from a metal atom to a non-metal atom.

• In practice, this never completely happens, but a compound such as caesium fluoride Cs+F- forms an ionic bond in which the electron transfer is nearly complete with close to 100% ionic character.

• In a hydrogen molecule Hz, the two hydrogen atoms are identical and form a covalent bond with 100% covalent character by equally sharing the bonded pair of electrons. However, in molecules such as HCI, the bonded pair of electrons is not shared equally.

Between the extremes of Ionic andcovalent bonding, there Hi a whole range of intermediate bonds, which have both Ionic and covalent contributions.

An ionic bond is often formed with some covalent character;

• the electron transfer is incomplete

• there is a degree of ele.ctron sharing.

A covalent bond is often formed with some ionic character:

• the electrons are not equally shared

• there is a degree of electron transfer.

Pola.risation in ionic compounds

A 100% ionic bond could only form by complete transfer of electrons from a metallic atom to a non-metallic atom. Many ionic compounds have a degree of covalency resulting from incomplete transfer of electrons.

This effect, called polarisation, occurs in ionic compounds with:

• a small + ion (cation) with a high charge density

• a large - ion (anion) with a low charge density.

GG

charge

Charge density

ionic radius

Charge/size ratio increases

• Polarisation is greatest when a small, highly-charged cation polarises a large anion.

• The electric field around a small cation distorts the electron shells around a large anion.

• As a result, electrons are attracted towards the cation, giving a degree of covalency (electron sharing).

Example

In: A1203, polarisation takes place between Al" and 02- ions:

Small AI'+ ion is highly charged.

02- ion is distorted and polarised resulting in partial covalent character.

A 'perfect' ionic compound would contain spherical ions. Here, the 02- is distorted.

Aluminium oxide is a compound of a metal with a non-rrretal-e+» ionic bonding.

• The small aluminium ion polarises the much larger oxide ion.

• The ionic bond in AI203 has a degree (?)f covalent character.


27

28

The nuclei of the atoms in a molecule attract the electrons pair in a covalent bond. It is this attraction which is responsible for the covalent bond.

In a hydrogen molecule, the nucleus of each hydrogen atom is attracted towards the electron pair of the covalent bond.

H H

Electronegativity is a measure of the attraction of an atom in a molecule for the pair of electrons in a covalent bond.

The most electronegative atoms attract bonding electrons most strongly.

• In general, small atoms are electronegative atoms.

• The most electronegative atoms are those of highly reactive non-metallic elements (such as 0, F and CI).

• The large atoms of reactive metals (such as Na and K) have the least electronegative atoms.

How is electronegativity measured?

,

The 'Pauling scale' is often used to compare the electronegativities of different elements. The diagram below shows how the electronegativity of an element relates to its position in the Periodic Table. The numbers give the Pauling electronegativity values.

elect:ronegativity increases
r Li Be B C N 0 F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na CI
0.9 3.0 I
K Br
0..8 2.8 See how the Pauling values of electronegativity relate to the element's position in the Periodic Table.

Fluorine, the most electronegative element has:

• an electronegativity of 4.0

• small atoms with a greater attraction for the pair of electrons in a covalent bond than larger atoms.

The greater the difference between electronegativities, the greater the ionic character of the bond.

The greater the similarity in electronegativities, the greater the covalent character of the bond.


Polar and non-polar molecules

Non-polar bonds

A covalent bond is non-polar when:

• the bonded electrons are shared equally between both atoms

• the bonded atoms are the same

• the bonded atoms have similar electronegativities.

A covalent bond mustbe non-polar if the bonded atoms are the same, as in the molecules of H2 and Cl, shown below.

ffi

H2 molecule

el2 molecule

Polar bonds

A covalent bond is polar when:

• the electrons in the bond are shared unequally

• the bonded atoms are different, each has a different electronegativity.

The bond in hydrogen chloride, H-CI, is predominantly covalent with one pair of electrons shared between the two atoms.

• However, the chlorine atom is more electronegative than the hydrogen atom.

• The chlorine atom has a greater attraction for the bonded pair of electrons than the hydrogen atom making the covalent bond polar.

6+~6-

H ~ CI

bonded pair of electrons attracted closer to chlorine

• The HCI molecule is polarised with a small positive charge b+ on the H atom and a small negative charge 0- on the Cl atom.

• The hydrogen chloride molecule is polarwith a permanent dipole

Symmetrical and unsymmetrical molecules

In symmetrical molecules, dipoles cancel and there is no overall permanent dipole .

• Each C-CI bond is polar but the dipoles act in different directions.

CCI. is non-polar 6-

CI

6- '-6+ 6- CI "'"IC-CI

eel/'

• The overall effect is for the dipoles to cancel each other.

Therefore CCI4 is a non-polar molecule.

Although each C-CI bond is polar, the dipoles cancel.

• When bonding atoms are the same, the attraction for the bonded pair of electrons is the same - the bond is non-polar.

• In a polar covalent bond, the bonded electrons are-attracted towards the more electronegative of the atoms - the bond is polar.


29

Intermolecular forces

Strength of bonds and forces

• Ionic, covalent and metallic bonds are of comparable strength.

• Intermolecular forces are much weaker.

type of bond bond enthalpy/ k] mol"
covalent bond 200-500
hydrogen bond 5-40
van der Waals' forces -2 van der Waals' forces

van der Waals' forces (induced dipole-dipole interactions) exist between all molecules whether polar or non-polar.

van der Waals' forces are:

• weak intermolecular interactions

• caused by attractions between very small dipoles in molecules.

Movement of electrons produces an oscillating dipole.

66+

dipole oscillates and continually changes with time

66- 66+

Oscillating dipole induces a dipole in a neighbouring molecule which is induced onto further molecules.

induced dipoles attract one another

What affects the strength of van der Waals' forces?

van der Waals' forces result from interactions of electrons between molecules. The greater the number of electrons in each molecule:

• the larger the oscillating and induced dipoles

Ii the greater the attractive forces between molecules

• the greater the van der Waals' forces.

Permanent dipole-dipole interactions

• Permanent dipole-dipole interactions are weak intermolecular forces

• They are simply attractions between weak dipole charges on different molecules.

weak dipole-dipole interactions

between HCI molecules 5+ 6-

6+ 6- 6+" /H-CI~

H-CI~H

\" 6

~ 5+ ~ ; ~

CI1 -H-CI ----CI

Between HC! molecules, there will be both van der Waals' forces and permanent dipoledipole interactions. Both are weak forces, but permanent dipole-dipole interactions> van der Waals' forces.

30

66-


Hydrogen bonds

A hydrogen bond is a special type of permanent dipole-dipole interaction found between molecules containing the following groups:

0+ u.§;.H-N

."'-

0+ 11-_ 0- H-.-:

••

A hydrogen bond is a comparatively strong intermolecular attraction between:

• an electron-deficient hydrogen atom, HO+, on one molecule and

• a lone pair of electrons on a highly electronegative atom of F, ° or N on another molecule.

Hydrogen bonding occurs between molecules such as H20:

A hydrogen bond is shown between molecules as a dashed line. Note the role of the lone pair - essential in hydrogen bonding.

hydrogen bond formed by attraction between dipole charges on different molecules

Hydrogen bonding is important in organic compounds containing -OH or-NH bonds: e.g. alcohols, carboxylic acids, amines, amino acids.

Special properties of water arising from hydrogen bonding

A hydrogen bond has only about one-tenth the strength of a covalent bond. However, hydrogen bonding is strong enough to have significant effects on physical properties, resulting in some unexpected properties for water.

The solid (ice) is less dense than the liquid (water)

• Particles in solids are usually packed closer together than in liquids.

• Hydrogen bonds hold water molecules apart in an open lattice structure. Therefore ice is less dense than water.

hydrogen bonds break

MELTING OF ICE ...

ice lattice collapses:

molecules move closer together

tetrahedral open lattice in ice

Solids are usually denser than liquids - but ice is less dense than water. H20 has a relatively high melting point and boiling point

• There are relatively strong hydrogen bonds between H20 molecules.

• The hydrogen bonds are extra forces, over and above van der Waals' forces ..

• These extra intermolecular forces result in higher melting and boiling points than would be expected from just van der Waals' forces.

• When the ice lattice breaks, hydrogen bonds are broken.

Hydrogen bonds act between:

• a lone pair H-O:, H-Nl: or H-F: and

• a hydrogen atom H-O, H-N or H-F- on a different-molecule.

When water changes state, the covalent bonds between the Hand 0 atoms in an H20 molecule are strong and do not break - the much weaker intermolecular forces break.


31

Metallic bonding

A metallic bond holds atoms together in a solid metal or alloy. In solid metals, the atoms are ionised.

• The positive ions occupy fixed positions in a lattice.

• The outer shell electrons are delocalised - they are spread throughout the metallic structure and are able to move freely throughout the lattice.

A metallic bond is the electrostatic attraction between the positive metal ions and delocalised electrons.

0-0-0 8-8-8-8 -0-8- 8

In the metallic lattice, each metal atom exists as a

positive ion by releasing its outer shell electrons to the 'sea of electrons'.

The 'sea of electrons '

Delocalised and localised electrons In a metallic bond:

• the delocalised electrons in metals are spread throughout the metal structure

• the delocalised electrons are able to move throughout the structure

• it is impossible to assign any electron to a particular positive ion.

In a covalent bond:

• the localised pair of electrons is always positioned between the two atoms involved in the bond

• the electron charge is concentrated between the bonded atoms.

Properties of giant metallic lattices

All metals form giant metallic lattices in the solid state.

A giant metallic lattice is held together by strong electrostatic attractions between positive ions and negative electrons.

High melting point and boiling point

• Generally, high temperatures are needed to separate the ions from their rigid positions within the lattice.

Therefore most metals have high melting and boiling points.

Good thermal and electrical conductivity

• The existence of mobile, delocalised electrons allows metals to conduct heat and electricity well, even is the solid state.

• The electrons are free to flow between positive ions.

• The positive ions do not move.

- - ~

0-0-0

- - - !!+

0-0-0-0

- - - - ..

0-0- 0 +

drift of delocalised electrons across potential difference

A metallic bond acts between the positive metal ions and delocalised electrons. When a metal conducts electricity, only the electrons move.

32


Giant ionic lattices

Ionic compounds form giant ionic lattices with each ion surrounded by ions of the opposite charge.

A giant ionic lattice (see p. 23) is held together by strong electrostatic attraction between positive and negative ions.

Properties of giant ionic lattices

High melting point and boiling point Ionic compounds are solids at room temperature.

• High temperatures are needed to break the strong electrostatic forces holding the

ions rigidly in the solid lattice.

Therefore ionic compounds have high melting and boiling points,

Electrical conductivity

In the solid lattice:

• the ions are in a fixed position and there are no mobile charge carriers. Therefore an ionic compound is a non-conductor of electricity in the solid state.

When melted or dissolved in water:

• the solid lattice breaks down

• the ions are now free to move as mobile charge carriers.

Therefore an ionic compound is a conductor of electricity in liquid and aqueous states.

Solubility

• The ionic lattice dissolves in polar solvents (e.g. water).

• The polar water molecules break down the lattice and surround each ion in solution as shown below for sodium chloride.

Na" attracts &- charges on the o atoms of water molecules.

• Water molecules attract Na+ and cr ions.

• Lattice breaks down as it dissolves.

• Water molecules surround ions.

Cl attracts b+ charges on the H atoms of water molecules.

• The strong forces between ions result in high melting and beilinq points.

• Ionic compounds conduct only when ions are free to move - when molten or in aqueous solution.

• Ionic compounds tend to dissolve in polar solvents such as water.


33

Properties of simple molecular structures

Elements and compounds with covalent bonds have either of two structures:

• a simple molecular structure

• a giant molecular structure.

Simple molecular structures

Simple molecular structures comprise small molecules, such as Ne, Hz, 0Zl Nz.

A simple molecular structure is held together by weak forces between molecules.

The atoms within each molecule are bonded strongly together by covalent bonds.

34

Properties of simple molecular structures Low melting point and boiling point

• Low temperatures provide sufficient energy to break the intermolecular forces. Therefore simple molecular structures have low melting and boiling points.

The different forces within the simple molecular structure of solid I, are shown below:

Strong covalent bonds hold

m IOgr \ mOlec"~

m mCb"'m~m

Weak van der Waals' forces between 12 molecules

When the simple molecular structure of 12 is broken:

• only the weak van der Waals' forces between the Iz molecules break

• the covalent bonds, I-I, are strong and do not break.


• There are no free charged particles.

Therefore simple molecular structures are non-conductors of electricity.

Solubility

• van der Waals' forces form between a simple molecular structure and a non-

polar solvent, such as hexane.

• These interactions weaken the structure.

Therefore simple molecular structures are soluble in non-polar solvents (e.g. hexane).

The properties of a substance depend upon its bonding and structure.

• Ionic and covalent bonds are of comparable strength - intermolecular forces are far weaker.

• van der Waals' forces increase in strength with increasing number of electrons.

• An oscillating or instantaneous dipole is caused by an uneven distribution of electrons at an instant of time.

• Simple molecular structure - weak forces break - low melting point.


Diamond, graphite and SrO, are common examples of giant molecular lattices. This type of structure is known by a variety of names: a giant molecular lattice, a giant covalent lattice, a giant atomic lattice and a macromolecular lattice.

A giant molecular structure is held together by strong covalent bonds between atoms.

Properties of giant molecular structures High melting point and boiling point

• High temperatures are needed to break the strong covalent bonds in the lattice. Therefore giant molecular structures have high melting and boiling points. Covalent bonds are strong. The covalent bond breaks when a giant molecular structure melts or boils - this only happens at high temperatures.


• Except for graphite (see below), there are no free charged particles. Therefore giant molecular structures are non-conductors of electricity.

Solubility

• The strong covalent bonds in the lattice are too strong to be broken by either polar or non-polar solvents.

Therefore giant molecular structures are insoluble in polar and non-polar solvents.

Comparison between the properties of diamond and graphite

property diamond graphite
tetrahedral hexagonal layers
symmetrical structure ~ strong layer
structure * held together by structure but with
strong covalent bonds weak bonds
,
. . throughout lattice , between the layers
. -
- -
- -
- -
poor conductivity good conductivity
electrical • There are no delocalised electrons • Delocalised electrons between
conductivity as all outer shell electrons are layers.
used for covalent bonds. • Electrons are free to move parallel
to the layers when a voltage is
a~~lied.
hard soft
hardness • Tetrahedral shape enables • Bonding within each layer is strong.
external forces to be spread • Weak forces between layers easily
throughout the lattice. allow layers to slide. • Covalent bonds break when a giant molecular lattice melts or boils.

• Giant structure - strong forces break - high melting point.


35

The different types of bonds and forces

• Covalent bonds act between atoms.

• Ionic bonds act between ions.

• Metallic bonds act between positive ions and electrons.

• Hydrogen bonds act between polar molecules.

• Dipole-dipole interactions act between polar molecules.

• van der Waals' forces act between induced dipoles of molecules.

Bonding, structure and properties

structure bonding m. pt. reason electrical reason solubility reason
lb. j:lt. conductivity
giant ionic ionic bonds high strong poor when ions in a good in attraction
electrostatic solid fixed polar between
attractions position solvents, ionic lattice
between in lattice e.g. water and polar
oppositely- solvent
charged good when lattice has
ions aqueous or broken down:
molten mobile ions
simple van der low weak van poor no mobile good in van der
molecular Waals' der Waals' charged non-polar Waals'
forces forces particles solvents forces
between (electrons between
molecules or ions) molecular
structure
and solvent
giant covalent high strong poor no mobile poor forces
molecular bonds covalent (except charged within
bonds gr,aphite) particles lattice tOG
between (electrons strong to
atoms or ions) be broken
b)' solvents
hydrogen hydrogen low but dipole- poor no mobile good in attraction
bonded bonds higher dipole charged polar between
than attractions particles solvents, dipoles
expected between (electrons e.g. water
atoms or ions),
giant metallic usually stronq good mobile poor forces within
metallic bonds high electrostatic electrons, lattice too
attractions even in strong to be
between solid state broken by
ions and solvents
electrons A high melting point is the result of any giant structure, bonded together with strong forces. Giant structures can be ionic, covalent or metallic.

36



1 Draw 'dot-and-cross' diagrams of (i) MgO

(ii) Nap.

2 Predict formulae for the following ionic compounds:

(a) lithium chloride (e) sodium carbonate

(b) potassium sulphide (f) calcium hydroxide

(c) lithium nitride (d) aluminium oxide

(g) aluminium sulphate

(h) ammonium phosphate.

3 Draw 'dot-and-cross' diagrams for (i) CZH6 (ii) HCN (iii) HP+.

4 For each of the following molecules predict the shape and bond-angles:

(a) BeFz (e) PH3

(b) AICI3 (f) CSz

(c) SiH4 (g) 503

(d) HzS (h) SOz'

5 Decide whether each molecule is polar and state which atom, if any, has the 0- charge.

(a) Brz (d) HBr

(b) Hp (e) NH3•

(c) 0z

6 (a) Predict the shape of a molecule of BF3 and of PFr (b) Explain why BF3 is non-polar whereas PF3 is polar.

7 Which of the following molecules have hydrogen bonding:

HP, HzS, CH4, CHPH, NOz?

8 Draw diagrams showing hydrogen bonding between: (a) 2 molecules of ammonia

(b) 1 molecule of water and 1 molecule of ethanol, CzHsOH.

9 For

(a) MgO (b) CH4 (c) Si02

state the structure and explain the following physical properties: melting and boiling points, electrical conductivity, solubility.

37

38

The Periodic Table

Arranging the elements In the Periodic Table:

• elements are arranged in order of increasing atomic number

• Groups are vertical columns including elements with similar properties

• Periods are horizontal rows across which there is a trend in properties.

Key areas in the Periodic Table

•

periods - trend in properties

metals

non-metals -<-----p block---+

III D
<V s block
t
<V
e,
0
"-
Co <II
"- ;<= d block
1"1:1 <II !?:'..
'E ;<= s·
~ It>
'iii It>
'"
:3 ;::!.
III It> :T transition elements
e, [ 3
::J '" It>
0 S
....
C"l v;- f block

rare-earths

• The diagonal stepped line separates metals (to the left) from non-metal (to the right).

• Elements close to this line, such as silicon and germanium, are called semi-metals or metalloids, They show properties intermediate between those of a metal and a non-metal.

• The four blocks (s, p ,d and f) show the sub-shell being filled. (See also p. 7)

Periodicity

Periodicity is the periodic trend in properties, repeated across each period,

E.g. Period 2 METAL----->- NON-METAL

Period 3 METAL- NON-METAL

This periodicity of properties means that predictions can be made about the likely properties of an element and its compounds.

Note the metal/non-metal divide.

• On descending the Periodic "fable, the changeover from metal to non-metal. takes place further to the right,

• At the top of Group 4 carbon is a non-metal- at the bottom of Group 4 tin and lead are metals.

This means that subtle trends in properties take place down each group.


..

I

Trends in.boiling point

Trends in boiling point provide information about structure: giant or simple molecular. Period 2

7000
¥ 6000
C 5000 Giant structure: on
'0 •
~ 4000 boiling, strong forces
~ 3000 are broken - high
:g 2000 simple molecules
1000 <IE .:. boiling paint.
0
Li Be B C N 0 F Ne
element
Period 3
4000
¥
c 3000 • Simple molecular
'0 structure: on boiling,
~ 2000
~ weak forces are
"0 1000 broken -low boiling
.Q
0 point.
Na Mg AI Si P S CI Ar
element Across a period:

• the boiling point increases from Group 1 to Group 4

• there is a sharp decrease in boiling paint between Group 4 and Group 5

• the boiling points are comparatively low from Group 5 to Group 8.

The sharp decrease in boiling point marks a change from giant structures to simple molecular structtu:es. Note the periodicity in boiling point: the trend for Period 2 is repeated across Period 3.

More details of the structures of these elements are shown below.

Li Be B C N2 02 F 2 Ne

giant structures molecular structures

iii

•

strong forces between atoms

Na Mg AI Si

weak forces between molecules

~ ~ C~ Ar

Comparison of the boiling points of the metals

Note the increase in boiling paints of the metals Na ~ AI in Period 3.

• The number of delocalised electrons in the lattice increases.

• This results in increasing attractive forces within the metallic lattice.

Na Mg AI
- - -@ --@-- ~--
0-0-0 @-@-<8
0-0-0-8 - - @-@--@-@-
<8-_<3-<8 =<3
0-0-0 - <8--<3- <3- - @--@-@-
- ionic charges increases

number of outer shell electrons increases

attraction increases: boiling point increases

The increasing number of delocallsed electrons in the lattice also explains the increase in electrical conductivity from Na ~ AI.


39

40

Trends in atomic radii

Across a period
Across a period, the atomic radius decreases:
@ @ @ @ @ @ @
Li Be B C N 0 F
3p+ 4p+ 5p+ 6p+ 7p+ 8p+ 9p+ number of protons increases

radius decreases

• the nuclear charge increases

• outer electrons are being added to the same shell

• the attraction between the nucleus and outer electrons increases. Therefore the atomic radius decreases across a period.

Down a group

Down any group, the atomic radius increases:

number of electron shells increase

shielding increases

atomic radius increases

• extra shells are added that are further from the nucleus

• there are more shells between the outer electrons and the nucleus leading to greater shielding of the nuclear charge

• the attraction between the nucleus and the outer electrons decreases. Therefore the atomic radius increases down a group.

Atomic radii and first ionisation energies

The reasons for the trends in atomic radii are similar to those explaining trends in first ionisation energies (p. 41).

Atomic radius increases down a group.


..

Trends in first ionisation energies

Ionisation energy depends upon:

• atomic radius

• nuclear charge

• electron shielding (see p. 8 for details).

He·~---------------

Each 'peak' marks a Ne....--noble gas (He, Ne, Ar) at the end of each period.

f,= \Ar

first ionisation energy

N

c

Q

B

Na

u

K

O+-------~------~r_--------~~----._--

o

20 atomic number

Each 'trough' marks an alkali metal (Li, Na, K) at the start of each period

Across a period

There is general increase in first ionisation energy across a period (see H-He; Li-Ne; Na ....... Ar).

• The nuclear charge increases giving greater attraction on the outer electrons.

• There is little variation in atomic radius.

• Electrons are added to the same shell that is the same order of distance from the nucleus.

• All elements in the period experience similar. electron shielding from inner shells.

• Each element in a period has the same number of inner shells.

Across a period, the increased nuclear Charge is the most important factor for the general increase in first ionisation energy across a period.

For details of the 2/3/3 pattern across a period, see p. 9.

------------------------~

Starting the next period

• There is a sharp decrease in first ionisation energy between the end of one period and the start of the next period (see He-Li; Ne-s-Na: Ar-K).

• This reflects the addition of a new shell with the resulting increase in distance and shielding ~

Down a group

• There is a decrease in first ionisation energy down a group (see He-Ne-Ar and other groups).

• Extra shells are added that are further from the nucleus.

• There are more shells between the outer electrons and the nucleus leading to greater shielding of the nuclear charge .

• The greater the attractive force, the greater the first ionisation energy.

• Across a period, increased nuclear charge is most important. ~ increased attraction ~ increased first ionisation energy.

• Down a group, increased distance and shielding are most important. -----;0. decreased attraction ~ decreased first ionisation energy.


41

II

•

I

42

Redox reactions

Oxidation and reduction were originally used for reactions involving oxygen.

• Oxidation is the gain of oxygen.

• Reduction is the loss of oxygen.

Nowadays, oxidation and reduction have a much broader definition in terms of electron transfer in a redox reaction (reduction and oxidation).

• Reduction is the gain of electrons.

• Oxidation is the loss of electrons.

Reduction and oxidation must take place together:

• if one species gains electrons

• another species loses the same number of electrons.

Half-equations

The formation of magnesium chloride from its elements is a redox reaction:

overall reaction Mg + Cl, ~ MgClz

The electron transfer that has taken place can be shown by writing half-equations:

electron transfer Mg ~ Mg2+ + Ze" oxidation (loss of electrons)

Cl, + 2e- ~ 2Cr reduction (gain of electrons)

Oxidising and reducing agents

• An oxidising agent removes electrons from another reactant.

• Non-metals are oxidising agents, e.g. Fz, Clz, 02'

• A reducing agent adds electrons to another reactant.

• Metals are reducing agents, e.g. Na, Fe, Zn.

In the example above,

• Mg is the reducing agent - it has reduced the Cl, to 2Cr by adding electrons.

• Cl, is the oxidising agent - it has oxidised Mg to Mgz+ by removing electrons.

Using oxidation numbers

species oxidation number examples
uncombined element 0 C, zero; Na, zero; 0" zero.
combined oxygen -2 Hp; CaO.
combined hydrogen +1 NH3, H,S.
simple ion charge 0(;1 ion Na+, +1; Mg2+, +2; Cl", -1.
combined fluorine -1 NaF, CaF1. Examples of applying oxidation numbers In COz' the overall charge is zero.

• There are 2 oxygen atoms, each with an oxidation number of -2, giving a total

contribution of -4.

• The oxidation number of carbon must be +4 to give the overall charge of zero. In N03-, the overall charge is 1-.

• There are 3 oxygen atoms, each with an oxidation number of -2, giving a total contribution of -6.

• The oxidation number of nitrogen must be +5 to give the overall charge of-1.

When applying oxidation numbers to elements, compounds and ions, the sum of the oxidation numbers must equal the overall charge


Using oxidation number with equations

By applying oxidation numbers to an equation:

• the species being oxidised and reduced can be identified.

• the number of electrons on both sides of the equation can be checked.

Cr2CMs) + 2 AI(s) -- AI,O~(s) + 2 Cr(s)
oxidation -+3 -2 0 +3 -2 0
numbers +3 -2 0 +3 -2 0
-2 -2
sum of oxidation ~ ~
numbers: 0 0 0 0 In this reaction, the changes in oxidation number are:

Cr: +3 -----.. 0 reduction oxidation number decreases

AI: 0 -----00 +3 oxidation oxidation number increases.

• Oxidation is an increase in oxidation number.

• Reduction is a decrease in oxidation number.

Combining half-equations

An overall equation for a redox reaction can be constructed by combining the halfequations showing the transfer of electrons in the reaction.

Example: The reaction of Ag+ ions with Zn metal

The half equations are:

Ag'(aq) + e

Zn(s)

-----00

+

--

To combine the half-equations in an overall equation:

• every electron lost by Zn(s) is gained by Ag"

• the number of electrons transferred must be the same in each half-equation

• the Ag" half-equation is multiplied by 'Z' to balance the electrons.

ZAg+(aq) + ze -----00 ZA~(s)

Zn(s) -----00 Zn "(aq) + Ze-

• The equations are now added:

ZAg+(aq) + Ze- + Zn(s) -----00 ZAg(s) + Zn2+(aq) + Ze-

• Any species appearing on both sides are cancelled to give the overall equation.

ZAg+(aq) + Zn(s) -----00 ZAg(s) + Zn2+(aq)

• Finally, check that the oxidation numbers balance on either side of the equation:

ZAg+(aq) + Zn(s) ----;0 ZAg(s) + Zn2+(aq)

oxidation numbers: + 1 0 0 +Z

+1 0

oxidation number check:

+Z

+Z

01 L Oxidation Is Loss of electrons

RIG Reduction Is Gain of electrons


43

44

The s-:block elements:'Group 1 and Group .2",

General properties

The elements in Group 1 and Group 2 have hydroxides that are alkaline and their common names reflect this.

• The Group 1 elements are the Alkali Metals

• The Group 2 elements are the Alkaline Earth Metals

Electronic configuration

The elements in Group 1 and Group 2 have their highest energy electrons in the s sub-shell and these two groups are known as the 's-block elements'

Each Group 1 element has:

• one electron more than the electronic configuration of a noble gas

• an outer s sub-shell containing one electron.

Each Group 2 element has:

• two electrons more than the electronic configuration of a noble gas

• an outer s sub-shell containing two electrons.

Electronic conti uration of the s-block elements

Grou~ 1 Group- 2

Na [Ne] 3s Mg [Ne

K [Ar] 45' Ca [Ar]

Rb [Kr] 5s Sr

Cs [Xe] 6s' Ba

Fr [Rn] 7s' Ra

----~~------------~

Physical properties

Group 1

• They are soft metals and can be cut with a knife.

• They have low melting and boiling paints.

• They have low densities: Li, Na and K all float on water.

• They have colourless compounds.

Group 2

• They have reasonably high melting and boiling points.

• They have low densities although higher than those in Group 1.

• They have colourless compounds.

Flame tests

When heated in a flame, compounds of Groups 1 and 2.show characteristic flame colours, allowing different cations to be identified.

cation u'

~fl_am __ e_c_o_lo_u_r re_d o __ range

lilac

brick-red green

--------~~

red

The characteristic flame colours arise from electronic transitions within the atom.

• Heat energy from the flame excites an electron to a higher energy level.

• The electron returns to a lower energy level.

• The excess energy is released as light energy.

• The frequency of the flame colour depends upon the difference between the energy levels involved.

• Within each group, the elements become more reactive descending the group.

• Within each period, the Group 1 element is more reactive than the Group 2 element.


...

Reactivity of the s-block elements

The elements in the s-block are the most reactive metals, strong reducing agents.

• Group 1 elements are oxidised in reactions.

• Each atom loses one electron from its outer s sub-shell to form a 1+ ion:

M ------.. M+ + e- (+1 oxidation state)

• Group Z elements are oxidised in reactions.

• Each atom loses two electrons from its outer s sub-shell to form a Z+ ion:

M -- MZ+ + 2e- (+Z oxidation state)

Reactivity increases down each group reflecting the increasing ease of losing electrons. The ionisation energy of the metal is an important factor in this process.

reactivity
increases
Li Be
Na Mg
K Ca reactivity
Rb Sr increases
Cs Ba
Fr Ra , The Group 1 elements

Reaction with oxygen

• The Group 1 elements react vigorously with oxygen.

• Each element forms the expected ionic oxide with the general formula, (M+)zOz-.

• On descending the group, further oxidation takes place ~ a mixture of metal oxides.

Lithium forms the expected oxide Li.O:

4Li(s) + 0z(g) -- ZLiz@(s)

,

-

Sodium forms a mixture of Na.O and the peroxide NazOz:

I ~ ~i,"rl.-~~.f

4Na(s) + 0z(g) -- ZN;f'ii::)(S),·l

ZNa(s) + 0z(g) ~ Napz(s)

Potassium forms a mixture of KzO, the peroxide KzOz and the superoxide KOz: 4K(s) + 0ig) -- ZKP(s)

ZK(s) + 0z(g) -- KPz(s)

K(s) + 0z(g) -- KOz(s)

Reaction with water

• The Group 1 elements react vigorously with water -----<> metal hydroxide + hydrogen.

• The metal hydroxides are alkaline

e.g. ZNa (s) + ZHP(l) -- ZNaOH(aq) + Hz(g)

• The Group 1 hydroxides are strong alkalis.

• The reactivity of the Group 1 elements increases down the group.

Group 1 oxides

Readion with water

• The Group 1 oxides react with water forming strongly alkaline solutions. e.g. NaP(s) + Hp(l) -- 2NaOH(aq)

Readion with acids

• The oxides behave as bases and are neutralised by acids -- salt + water e.g .. NaP(s) + ZHCl(aq) -- ZNaCI(aq) + Hz0(l)

Reactivity of the Group 1 elements increases down the group because:

• their first ionisation energies decrease

• it becomes easier to remove the outer electron from their atoms.


45

46

Reaction with oxygen

• The Group 2 elements react vigorously with oxygen .

• Each element forms the expected ionic oxide with the general formula, MZ+Oz-.

E.g. 2Ca(s) + 0z(g) ----c. 2CaO(s)

Be Mg Ca Sr Ba Ra

Action of water

• Reactivity with water increases down the group.

• This reflects the increasing ease with which electrons can be lost.

Mg reacts very slowly with water, forming the hydroxide and hydrogen:

Mg(s) + 2Hz0(l) ----+ Mg(OH)z(aq) + Hz(g)·

With steam, reaction is much quicker forming the oxide and hydrogen:

Mg(s) + HzO(g) ----+ MgO(s) + Hz(g)

Further down the group from calcium, each metal reacts vigorously with water:

Ca(s) + 2HzO(1) ----+ Ca(OH)z(aq) + Hig)

reactivity

as reducing agent increases

Group 2 oxides

Reaction with water

• The Group 2 oxides form weakly alkaline solutions with water e.g. MgO(s) + Hp(l) ~ Mgz+(aq) +. 20H-(aq)

Reaction with acids

• The oxides and hydroxides are bases: - neutralised by acids ~ salt + water: e.g. MgO(s) + 2HCI(aq) ----+ MgClz(aq) + Hp(l)

Solubility of Group 2 hydroxides and sulphates Solubility of hydroxides

Group 2 hydroxides dissolve in water ~ alkaline solutions:

e.g. Ba(OH)z(s) + aq ~ Baz+(aq) + 20H-(aq)

The solubility of the hydroxides in water increases down the group and resulting solutions are more alkaline.

• Mg(OH)z(s) is only slightly soluble in water - the resulting solution is a weak alkali.

• Ba(OH)z(s) is much more soluble in water - the solution formed is more alkaline with a greater OH-(aq)

concentration than from Mg(OH)z.

Hydroxides

Mg(OH)2 solubility

increases

Ca(OH)2 Sr(OH)2 Ba(OH)2

alkalinity increases

Solubility .of sulphates

• The solubility of the sulphates in water decreases down the group.

• ·Magnesium sulphate MgS04 is very soluble.

• Barium sulphate BaS04 is Virtually insoluble.

• In the laboratory, the precipitation of BaS04 is used to MgSO.

test for the sulphate ion. CaS04

• BaCI/aq) or Ba(N03)z is added to a solution of a SrSO.

substance in dilute nitric acid. BaSO.

• In the presence of sulphate ions, a dense white L.- .......

precipitate of barium sulphate is formed:

Ba2+(aq) + SO 42-(aq) ----+ BaS04(s)

Sulphates

solubility

increases

For hydroxides, selubility increases down Group 2. For sulphates, solubility decreases down Group 2.


The thermal stability of s-block compounds

The s-block carbonates Group 2 carbonates

The Group 2 carbonates are decomposed by heat: e.g. MgC03(s) ~ MgO(s) + COz(g)

. This is caused by the polarising effect of the Group 2 cation:

MgC03 CaCOJ SrC03 BaCO,

ease of thermal decempesltlon decreases

• It is increasingly more difficult to decompose the carbonate as the group is descended.

• Down the group the polarising power of the metal cation decreases as the

charge: size ratio decreases.

Polarisation occurs when a small cation distorts the electron shells of a larger anion. The polarising effect is greatest between:

• a small densely charged cation

• and a large anion. (See also p. 27)

Group 1 carbonates

Except for LiZCOy the Group 1 carbonates are not decomposed by heat. The cations in the y.wu.R 1 carbonates are larger than those of the Group 2 carbonates - their polarisftrg power is less.

Lithium carbonate iSdecomposed by heat:

LizC03(s) -----.. LizO(s) + COz(g)

• The Li" ion is comparable in size with the Mi+ ion.

• Li" has a greater polarising power than the other Group 1 cations.

The s-block nitrates Group 2 nitrates

The Group 2 nitrates are decomposed by heat, releasing NOz and 02 gases: e.g. Ca(N03\(s) ~ CaO(s) + 2NOz(g) + %02(g)

On descending the group, as with the Group 2 carbonates:

• the nitrates become more thermally stable

• the increasing size of the cations results in a decrease in polarising power.

G.roup 1 nitrates

Except for LiN03, the Group 1 nitrates decompose with heat releasing only oxygen gas:

e.g, NaN03(s) ~ NaNOz(s) + Y202(g)

However, as with the carbonates above:

• the smaller Li" ion has a greater polarising power than other Group 1 cations

• lithium nitrate is decomposed by heat in a similar way to the Group 2 nitrates:

2LiN03(s) ~ Li20(s) + 2N02(g) + %02(g)

With heat, Li2C03 and LiNO] behave Similarly to the carbonates and nitrates <!)f magnesium. This is known as a diagonal relationship

You can see why by comparing the positions of Li and Mg in the Periodic Table.


47

48

The Group 7 elements and their compounds

General properties

The common name for the elements in Group 7 is the Halogens

Electronic configuration

Each halogen has seven outer shell electrons, just one electron short of the electronic configuration of a noble gas.

The outer p sub-shell contains five electrons.

Trend in physical states

. The outer p sub-shell
of the halogens
F ;Zp~
CI 3p'
Br 4p~
I s.~
At 6ps The halogens exist as diatomic molecules, X2• The boiling points of the halogens increase on descending the group.

• The physical states of the halogens at r.t.p. show the

" classic trend of gas ~ liquid ~ solid.

• On descending the group the number of electrons increases leading to an increaseIii the van der"Waals'

\ , <:::: ----

forces between molecules. -----

.,..----

Therefore boiling point increases.

F2 gas o, gas Br2 liquid

12 solid

Atz

solid

boiling point

increases down group

Reactivity of the halogens as oxidising agents

The halogens are the most reactive non-metals and are strong oxidising agents.

• The halogens are reduced in reactions.

• Each atom gains one electron into a p sub-shell to form a 1- ion:

e.g. YzFig) + e" ~ F-(g)

reactivity

(-1 oxidation state)

as Qxidisin§l agent inereases

• The halogens become less reactive as the group descends as

their oxidising power decreases

On descending the halogens:

• atomic radius increases

• shielding increases

• the nuclear attraction experienced at the edge of the atom decreases.

Oxidising power is a measure of the strength with which an atom is able to attract and capture an electron.

Displacement reactions of the halogens

The decrease in reactivity as the group is descended can be demonstrated by displacement reactions of aqueous halides using Cl., Br, and 12,

chlorine oxidises both Br- and I-

• Clz(aq) + ZBr-(aq) ~ ZCr(aq)' + Br2(aq)

• Clz(aq) + Zr(aq) - Z'tr(aq) + Iz(aq) bromine oxidises 1- only

• Brz(aq) + Zr(aq) -----.. ZBr-(aq) + Iz(aq) iodine does not oxidise either cr or Br

Fluorine is the strongest oxidising aqent.

• It is able to attract an extra electron more strenqiy than other haloqens,

• This attraction decreases down the group as the atornsqet bigger.

• Therefore the mddising power of the halogens decreases down the qroup.

.1


"

> ' •• I .r ': ~ ',,: ',:':""

.' Halides:· \~~ .

. " . .,', ..

Testing for halide ions

• Add aqueous silver ions, using AgN03(aq).

• Halide ions form coloured precipitates with different solubilities in aqueous

ammonia.

chloride: Ag'(aq) + ClIaq) -- AgCI(s) white precipitate, soluble in dilute NH3Caq) bromide: Ag'(aq) + Br'{aq) -- AgBr(s) cream precipitate, soluble in conc NHiaq) iodide: Ag+(aq) + F(aq) -- AgI(s) yellow precipitate, insoluble in conc NH3(aq)

Reactions of halides w,ith concentrated sulphuric acid

• Concentrated sulphuric acid is an oxidising agent.

• Halide salts reduce concentrated sulphuric acid producing a range of products depending on the halide used.

• The reducing power of the hydrogen halides increases as the halogens are descended.

. i ncreased

Hel strength

HBr as

HI reducing

agent

NaC. and H2S04

J Hydrogen chloride gas, HCI, is formed,

NaCl(s) + H2S04(l) -- NaHSO/s) + HCI(g)

\l • The HCI formed is not a sufficiently strong reducing agent to reduce the

sulphuric acid.

• No redox reaction takes place

NaBr and H2S04

Hydrogen bromide gas, HBr, is initially formed.

NaBr(s) + HzS04(l) -- NaHSOis) + HBr(g)

Some of the hydrogen bromide reduces the sulphuric acid with the formation of sulphur dioxide and orange bromine fumes,

ZHBr(g) + HzS04(1) -- SOz(g) + BrzCg) + ZHz0(l)

+6 -Z +4 5 reduced

Z x -1 ----'-+Z"'- __ ----'*

Z x 0 Br oxidised

Nal and H2S04

Hydrogen iodide gas, HI, is initially formed.

Nal(s) + H2S04(1) -- NaHS04(s) + HI(g)

Hydrogen iodide is a strong reducing agent and reduces the sulphuric acid to a mixture of reduced products including sulphur dioxide and hydrogen sulphide.

Reduction to 502 (ox no: +4) ZHI(g) + HzS04(l) -+6 __ -=Z_

+4

5 reduced Z x 0 I oxidised

Z x -1 +-'-'Z"'-- __ ---->-

Further reduction to H;r5 (ox no: -2)

6HI(g) + S0zCg) -- HzS(g) + 3Iz(s) +. ZHz0(l) -Z

+4 ----=-----'*

-Z

5 reduced

6 x -1 -'-+=Z ----'*

6 x 0 I oxidised

Increasing reducing power of hydrogen halide

HI reduces H2S04 and S02 HzS04 HI, 12 + S02

SOz Hl. 12 + HzS

HCI does not reduce HZS04


49

I

, I

50

Uses of chlorine

Small amounts of chlorine are added to drinking water to kill bacteria that would make the water unsafe to drink. Stronger solutions of chlorine in water are in equilibrium:

Clz(aq) + Hz0(l) ~ HClO(aq) + HCI(aq)

HCIO (chloric(I) acid) acts as a bleach and, if indicator solution is added, the initial red colour (from the acids) disappears as the bleaching action takes place.

The formation of bleach

Bleach is formed when dilute aqueous sodium hydroxide and chlorine are allowed to mix at room temperature.

This reaction is an example of disproportionation in which chlorine is both reduced (to chloride, Cl") and oxidised (to chlorate(I) ClUJ.

Cliaq) + ZNaOH(aq) ~ NaCI(aq) + NaCIO(aq) + HzO(l)

-1

o

-1

chlorine reduced

+1

o

+1

chlorine oxidised

Further disproportionation of the chlorine takes place with hot, concentrated sodium hydroxide:

3NaClO(aq) ~ ZNaCI(aq) + NaCI03(aq)

__ -_4=---_ ..... Z x -1

2 x +1

chlorine reduced

+4

+S

chlorine 'oxidised

+1

The industrial extraction of chlorine

Chlorine is manufactured by electrolysis of a concentrated solution of sodium chloride (purified saturated brine).

The cell reactions are:

at the cathode ZHP(l) + Ze- ~ 20K(aq) + Hz(g)

at the anode 2Cqaq) -----;0. Clz(g) + Ze-

• Chlorine reacts with hydroxide ions (see above).

In the modern 'Membrane cell', a membrane keeps these two products apart, preventing any reaction.

• The other products are hydrogen and the alkali, sodium hydroxide.

• The process consumes" large amounts of electricity, which is the main expense.

Industrial extraction of bromine

The main source of bromine is as bromide ions, Br" in sea water.

• Bromine is extracted by oxidising sea water with chlorine.

• Chlorine is a stronger oxidising agent than bromine - it displaces the bromide ions in a displacement reaction (see also page 48).

C12(aq) + ZBr~(aq) ~ 2Cr(aq) + Brz(aq)

Dispreportionatlon is simultaneous oxidation and reduction of the same species in a redox reaction.


.. '

lodine-thiosulphate titrations

• Iodine-thiosulphate titrations can be used to determine iodine concentrations, either directly or by liberating iodine using a more powerful oxidising agent.

• Iodine oxidises thiosulphate ions:

I2Caq) + 2SZ03Z-Caq) -- 2r(aq) + S4062-(aq)

• Thiosulphate is added from the burette to the iodine solution until the deepbrown colour of iodine becomes a light-straw.

• Starch is now added, forming a deep-blue colour.

• Thiosulphate is then added dropwise until the deep-blue colour becomes colourless. This is the end-point.

The estimation of chlorine in a. bleach

10.0 crrr' ofa sample of bleach was diluted to 250 cm'' with water; 25.0 em:' of this solution was pipetted into a flask.

An excess of aqueous potassium iodide was then added to liberate iodine:

equation 1 Clz(aq) + 2r(aq) -- liaq) + 2Cqaq)

Titration of this solution required 23.2 cnr' of 0.100 mol dm" sodium thiosulphate:

equation 2 2S20tCaq) + Iiaq) -- 2r-(aq) + S4062-(aq)

Calculate the concentration of chlorine in the bleach.

From the titration results, amount (in moles) ofNa~P3 can be calculated: amount (in moles) of NaZSp3 = c x 1600 = 0.100 x tg6~ = 0.00232 mol

From the equations, the amount (in moles) of Cl2 can be determined:

From equation 2, 2 mol SZ032- reacts with 1 mol 12

:. 0.00232 mol S}J32- reacts with 0.0~32 mol r, = 0.00116 mol Iz

From equation 1, 1 mol ci, forms 1 mol Iz

:. amount (in moles) of Cl, = 0.00116 mol

The concentration in mol dm-3 of the diluted bleach solution can be calculated by scaling to 1000 em':

25.0 ern" of diluted bleach contains 0.00116 mol Cl.,

1 ern" of diluted bleach contains 0.Og~16 mol Cl.,

1 dm'' of diluted bleach contains 0.00116 x 1000 = 0.0464 mol Cl.; 25

Finally, take into account the dilution with water {rom 10 cm3' to 250 em':

The original bleach was diluted by a factor of 21500 = 25

:. concentration of Cl, in bleach is 25 x 0.0464= 1.16 mo'l dm' .

An iedine-thiosulehate titration is an example of a redox titration. In this process:

• iodine is reduced: 12 + Ze -- 21- (0 -- -1)

• sulphur is oxidlsed 2Spt ~ s~ot + 2e- (+2 ~ + 2.S)

AS Chemistry Revision Notes 51

Ii II I II' I,

52

The main methods for extracting metals from their ores are:

• reduction of the ore with carbon

• reduction of the molten are by electrolysis

• reduction of the ore with a more reactive metal.

Reduction of iron oxide with carbon

The main are of iron, haematite, contains FeZ03 - reduced by coke in the blast furnace.

• This is a continuous process in which high quality haematite, coke and limestone are fed in at the top of the furnace and hot air is blown in near the bottom.

• Initially, hot coke reacts with air forming carbon monoxide: 2C(s) + 0z(g) - 2CO(g)

• The carbon monoxide reduces most of the iron oxide at around 1200°C:

FeZ03(s) + 3CO(g) - 2Fe(l) + 3C02(g)

• In hotter parts of the furnace, coke also reacts directly with iron oxide: 2FezOis) + 3C(s) -----: 4Fe(l) + 3C02(g)

This equation represents the overall reaction for the reduction.

The limestone is used to remove acidic impurities such as silicon dioxide (sand). This produces a slag, largely of calcium silicate, CaSi03:

CaC03 + Si02 - CaSi03 + CO2

• Molten iron collects at the bottom of the furnace and is run off as 'pig iron'.

• Pig iron is very impure and brittle - contains about 4% C (as well as Mn, Si, P and S).

Reduction of aluminium oxide using electrolysis

Except at very high temperatures, carbon does not reduce metals more reactive than zinc - these metals are usually extracted by electrolysis of the molten are.

• The main are of aluminium, bauxite, contains A1203• Purified bauxite is dissolved in molten cryolite (Na3AIF6) at 970°e.

• This is a continuous process needing regular additions of aluminium oxide.

The electrodes are made of graphite and the cell reactions are:

at the cathode A13+ + 3e- -------'.> Al

at the anode 202- - 02 + 4e-

• Periodically the graphite anodes need replacing because, at the high temperatures used, the carbon anodes react with the liberated oxygen.

2C + 02 - 2CO and C + 02 - CO2

Reduction of metal halides with metals

Some metals, such as titanium, become brittle unless very pure.

Highly pure metals can be formed by reduction of a metal halide with a reactive metal in a batch process.

• The main ore of titanium, rutile, contains TiOz which is first converted to TiCI4:

Ti02 + 2C + 2Clz - TiCl4 + 2CO

• For titanium, the chloride is reduced by a more reactive metal such as Na or Mg:

TiCl4 + 4Na - Ti + 4NaCI

The cost of the reducing agent - carbon (from coal) is cheap and is used where possible. The energy costs for the process - high temperatures and electrolysis are expensive,

The purity required of the metal- expensive to produce a very pure metal - must be balanced by high demand.


1 Using ideas about nuclear charge, attraction and shells, explain the trend in atomic radii across a period and down each group.

2 Why is the melting point of carbon much higher than that of nitrogen?

7 Identify the oxidation number changes taking place during the thermal decomposition of sodium nitrate:

2NaN03(s) -.. 2NaN02(s) + °2(g)

8 State and explain the trend in boiling points of the halogens fluorine to iodine.

9 How could you distinguish between NaCl, NaBr and Nal by a simple test?

10 Comment on the changes in oxidation number of chlorine in following reaction:

CI2(aq) + HP(I) -.. HCIO(aq) + H'(aq) + Cl'{aq)

3 What is the oxidation state of the species in the following:

(a) Ag+ (d) Fe

(b) F2 (e) MgF2

(c) N3- (f) NaCIO/

4 Write down the oxidation number of sulphur in the following.

(a) H2S (d) 5°32-

(b) 502 (e) Na2Sp3

(c) 50/-

5 The fol.lowing reaction is a redox process:

Mg + 2HCI -.. MgCI2 + H2

(a) Identify the changes in oxidation number.

(b) Which species is being oxidised and which is being reduced? (c) Identify the oxidising agent and the reducing agent.

6 Write down equations for the following reactions: (a) the reaction of barium with water

(b) the reaction of calcium oxide with nitric acid.


53

, ,"

"

Iii

i~

j:

~[

I

54

Chemical energetics

Enthalpy changes

Enthalpy, H, is the heat energy that is stored in a chemical system.

Enthalpy cannot be measured experimentally. However, an enthalpy change can be measured from the temperature change in a chemical reaction.

An enthalpy change MI is the heat energy exchange with the surroundings at constant pressure.

Exothermic reactions

• During an exothermic reaction, heat energy is released to the surroundings.

• Any energy loss from the chemicals is balanced by the same energy gain to the surroundings, which rise in temperature.

'\ r---t .:»

Enthalpy, H

Energy gain by the surroundings (identified by a temperature rise: t. THe)

reactants

Energy loss

during reaction ~

t.H -ve

products

reaction pathway

In an exothermic reaction:

• Mf is negative

• heat is given out (to the surroundings)

• reacting chemicals lose energy.

Endothermic reactions

• During an endothermic reaction, heat energy is taken in from the surroundings.

• Any energy gain to the chemicals is provided by the same energy loss from the surroundings, which fall in temperature.

products

Energy gain

during reaction .....-

Enthalpy, H

reactants

t

Energy Joss from the surroundings (identified by a temperature fall: 11 T -ve)

reaction pathway

In an endothermic reaction:

• 6H is positive

• heat is taken in (from the surroundings)

• reacting chemicals gain energy.

Remember what happens to the energy.

Exothermic IlH -ve

Endothermic IlH +ve

chemicals lose ener.gy chemicals gai"nenergy

surroundings get hotter. surroundings get colder.

•

•


, -

Standard enthalpy changes

Standard conditions

t!,.Hf:} refers to an enthalpy (H) change (t!,.) under standard conditions (f:}). Standard conditions are:

• a pressure of 100 kPa

• a stated temperature Z98K (ZS°C) is usually used

• a concentration of 1 mol dm" (for aqueous solutions).

A standard state is the physical state of a substance under standard conditions. The standard state of water at Z98K and 100 kPa is a liquid.

Standard enthalpy change of reaction

The standard enthalpy change of reaction !lIf&r is the enthalpy change that accompanies a reaction in the molar quantities expressed in a chemical equation under standard conditions, all reactants and products being in their standard states.

The equation matters:

HzCg) + Yz0ig) - Hz°(l) , t!,.Hf:}r = -286 kJ marl

1 mol Yz mol 1 mol

but with twice the quantities, there is twice the enthalpy change:

ZHz(g) + Dig) - ZHzO(l) t!,.Hf:}r = -572 kJ marl

Z mol 1 mol Z mol

Standard enthalpy change of combustion

The standard enthalpy change of combustion t!,.H&c is the enthalpy change that takes place when one mole of a substance reacts completely with oxygen under standard conditions, all reactants and products being in their standard states.

The combustion of 1 mole of ethane is represented as:

CZH4(g) + 30z(g) - ZCO/g) + ZHz0(l)

1 mol - combustion products

Standard enthalpy change of formation

The standard enthalpy change of formation t!,.H&f is the enthalpy change that takes place when one mole of a compound in its standard state is formed fr.om its constituent elements in their standard states under standard conditions.

The formation of 1 mole of water is represented as:

Hz(g) + lIz02(g) - HzO(l) t!,.Hf:}f = -Z86 k] mol"

elements - 1 mol

• For an element, the standard enthalpy change of formation is defined as zero.

For t!,.Hf:}cl 1 mole of a compound is completely burnt forming combustion products. For t!,.Hf:}f' 1 mole of a compound 'is formed from its elements.

For an element, t!,.H&f = O.


55

Direct determination of enthalpy changes

Calculating enthalpy changes

The heat energy change, Q, in the surroundings can be calculated using the relationship:

Q = mel'!.T Joules

• m is the mass of the surroundings that experience the temperature change.

• c is the specific heat capacity of the surroundings.

• I'!.T is the temperature change (final temperature - initial temperature).

Example

Addition of an excess of magnesium to 100 crrr' of 2.00 mol dm? CuS04(aq) raised the temperature from 20.0 °C to 65.0 "C. Find the enthalpy change for the reaction:

Mg(s) + CuS04(aq) -----0. MgS04(aq) + Cu(s) specific heat capacity of solution c = 4.18 J g-l K-1

density of solution = 1.00 g em",

Find the energy change

100 em" of solution has a mass of 100 g Temperature change, tlT

Energy gain to surroundings, Q = mcs'T

= (65.0 - 20.0) °C = +45.0 °C

= 100 x 4.18 x 45.0 J = +1881OJ

= -18810 J

:. energy loss from the reacting chemicals Find out the amount (in moles) that reacted

Amount (in mol) of CuS04 that reacted = 2.00 x loOoOo mol

= 0.200 mol

Scale the quantities to those in the equation Mg(s) + CuS04(aq) ----.. MgS04(aq)

1 mol 1 mol 1 mol

.'. 0.200 mol (1/5th mol) of CuS04

.'. 1 mol of CuS04

+ Cu(s)

1 mol

= Mf of -18810 J

= Mf of 5 x -18810 = "':'94050 J Mf = -94.1 kJ mol" (to 3 sig. figs.)

Enthalpy change of reaction is given by:

Mg(s) + CuSOiaq) -----0. MgS04(aq) + Cu(s) Mf= -94.1 k] mol"

- '---

For the surroundings: Q = mel'!. T Joules

• If the surroundings get hotter, they gain energy:

Q is positive and tlH is negative: chemicals lose energy exothermic reaction

• If the surroundings get wider, they lose energy:

Q is negative and I'!.H is positive: chemicals gain energy endothermic reaction

56 AS Chemistry Revision Notes

Enthalpy is stored within chemical bonds and bond enthalpy indicates the strength of a chemical bond in a gaseous molecule.

R-R(g) ------.. 2R(g) Mi = +436 kl marl R-CI(g) ------.. R(g) + CI(g) Mi = +432 k] marl

Bond enthalpy is the enthalpy change required to break and separate 1 mole of bonds in the molecules of a gaseous element or compound so that the resulting gaseous species exert no forces upon each other.

Average bond enthalpies

Bond enthalpies such as those above (H-H and H-CI) apply to specific compounds. However, some bonds can have different strengths in different environments.

The CI atom in CH3CI affects the environment of the C-H bonds.

H

I H-C-H

~\

H

I H-C-CI

I~

C-H bonds have different strengths and different bond enthalpies

• Data books provide an indication of the likely bond enthalpy of a particular bond by listing average or mean bond enthalpies.

• An average bond enthalpy indicates the strength of a typical bond.

Bond making and bond breaking

Chemical reactions involve bond-breaking followed by bond-making,

• Energy is first needed to break bonds in the reactants.

Bond breaking is an endothermic process and requires energy.

• Energy is then released as new bonds are formed in the products.

Bond making is an exothermic process and releases energy.

Using bond enthalpies to determine enthalpy changes For a reaction involving simple gaseous molecules:

• enthalpy required to break bonds = ~ (bond enthalpies of reactants)

• enthalpy released to make bonds = -L (bond enthalpies of products).

Mi = L (bond enthalpies of reactants) - L (bond enthalpies of products)

For the reaction: CH4(g) + 20z(g) ~ CO2(g) + 2HzO(g),

H H, ....... H
I 0=0
H-C-H + ~ o=c=o + 0
. I 0=0 H, ....... H
H 0
4 (C-H) + 2 (0=0) 2 (C=O) + 4 (O-H)
Milk] marl (4 x 413) + (2 x 497) (2 x 740) + (4 x 463) Bonds broken: (endothermic) Bonds made: (exothermic)

Mi = L (bond enthalpies of reactants) - L (bond enthalpies of products)

:. Mi = [ (4 x 413) + (2 x 497)] - [(2 x 740) + (4 x 463) ] k] marl

= -686 kJ marl

• Bond enthalpy is an endothermic change (t.H +ve) for bonds being broken.

• When bonds are made,

the enthalpy change will be the same magnitude but the opposite sign (t.H -ve).


57

Hess's Law

• Many reactions have enthalpy changes that cannot be found directly from a single experiment.

• Hess's Law provides a method for the indirect determination of enthalpy changes.

Hess's Law states that, if a reaction can take place by more than one route and the initial and final conditions are the same, the total enthalpy change is the same for each route.

Using llH-e-.: values to find an enthalpy change indirectly Example:

Find the enthalpy change for the reaction:

C(s) + 2Hz (g) ~ CHig)

Use the llHsc data as a 'link' to construct an energy cycle.

• An energy cycle is constructed by linking the reactants and products to their combustion products.

• Note the direction of the arrows from the reactants and products of the reaction to the common combustion products.

C(s) + 2HAg)

ROUTE 2

Calculate the unknown enthalpy change By Hess's Law, Route 1:

Route 2:

1'lH + [(-890)] [(-394) + (2 x -286)]

:. 1'lH + [(-890)] ;;

[(-394) + (2 x -286)]

Route 1

. Route 2

:. 1'lH;; [(-394) + (2 x -286)] - [(-890)] :. 1'lH;; -76 kJ mol'

:. C(s) + 2HzCg) -----+ CH4{g)

For enthalpy changes of cornbusticn data only:

tlH ;; .~tlHsc (reactants) - ~ llH&~ (products)

58


Using fl.H~ values to find an enthaipy change indirectly Example

Find the enthalpy change for the reaction:

C2H6(g) + 3Yz02(g) ---;. 2COz(g) + 3 Hz0(l)

substance C2H6(g) CO2(g) H 0(1)

/5.J:f""f I I<J mol-1 -85 -394

Use the flHBf data as a 'link' to construct an energy cycle .

• An energy cycle is constructed linking the reactants and products with their constituent elements .

• Note the direction of the arrows from the constituent elements to the reactants and products of the reaction.

ROUTE 2

Calculate the unknown enthalpy change By Hess's Law, Route 1:

Route 2:

[(-85) + (3Yz x O)J + MI [(2 x -394) + (3 x -286)J

AS Ch .

emlstry Revision Notes

:. [(-85) + 0] + tJ.H = [(2 x -394) + (3 x -286)]

Route 1

Route 2

:. tJ.H = [(2 x -394) + (3 x -286)] - [(-85) + 0] :. tJ.H = -1561 k] marl

C2H6(g) + 3Yz02(g) -----<> 2C0zCg) + 3H2°(l)

flHG = -1561 k] mol?

For enthalpy changes of formation data only:

flH = k AH&f (products) - k llH&f (reactants)

Hess's Law is simply an extension of the conservation of energy.

• The first law of thermodynamics states that energy may be exchanged between a chemical system and the surroundings but the total energy remains constant.

• Hess's Law accounts for the energy changes from the different routes.

59

5
II "
!'!i 1
t:: ,
~II
~il
l'1
li I
~I
~I
~l
~I
~f 6
u I

III

. .

Progress check

1 Draw energy profile diagrams for the following reactions:

(a) NPig) -- 2NOlg) IJ.H", +58 kJ rnol '

(b) N2(g) + 3H2(g) -- 2NH/g) IJ.H '" -92 k] mol"

2 Write an equation to represent the enthalpy change for: (a) IJ.H6-c (CH4)

(b) tlH6:f (NOz)

3 Addition of zinc powder to 55.0 ern' of aqueous coppertll) sulphate at 22.8 "C raised the temperature to 32.3 "C, 0.31 75 9 of copper were obtained.

(a) Calculate the energy released in this reaction.

'(b) Write an equation, including state symbols, for this reaction.

(c) Calculate the enthalpy change for this reaction per mole of copper formed.

4 Combustion of 1.60 9 of ethanol, C2HsOH, raised the temperature of 150 9 of water from 22.0°C to 71 .O°c. Find the enthalpy change of combustion of ethanol (c'" 4.18 J g-' K-').

You are provided with data for the following reaction:

Hig) + lig) ->- 2HI(g) tlH = +53 k] mol?

Hig) + Ilg) ->- 2H(g) + 21(g) tlH = + 183 kJ mol"

(a) Draw an energy profile diagram for this reaction showing both these energy changes.

(b) Use your diagram to find out how much energy is released during bond formation in this reaction.

(c) In this reaction, what can be deduced about the relative strengths of the bonds that are broken and the bonds that are formed?

Use the bond enthalpy data below to find the enthalpy change for each reaction. (a) C2H4(g) + 30/g) ---'-->' 2CO/g) + 2HP(g)

(b) Nig) + 3H/g) ------;0. 2NH3(g)

bond

C-H c=o 0=0 O-H C=C C-C N=N H-H N-H

average bond . 413 +740 +497 +463 +612 +347 -+,945 +436 +391

entha/eY./k] mor'_+ .....

7 Use the tlH6-( data below to calculate enthalpy changes for: (a) 3CCs) + 4H2(g) -- C3HsCg)

(b) CCs) + 2Hig) + Yz02(g) ->- CHpH(I)

substance C(s)

8 Use the IJ.H6-f data below to calculate enthalpy changes for: (a) C2H4(g) + H2(g) ->- C2H6(g)

(b) S02(g) + 2Hz5(g) ->- 2Hp(l). + 35(s)

-286

. HP(I) ,

Answers on page 92

60


ates and equi ibrium

What affects a reaction rate?

The rate of a reaction may be affected by the following factors:

• the concentration of the reactants

• the surface area of solid reactants Rather than use

• a temperature change

• the presence of a catalyst.

How does reaction rate change during a reaction?

For a reaction: A ~ B,

ti t change of concentration

reac IOn ra e = --"""----:.------

time

units: mol dm" S-l.

The reaction rate can be measured as:

• the rate of decrease in concentration of A

• the rate of increase in concentration of B.

The graphs below show how the concentrations of A and B change during the course of the reaction: A ------;. B

concentration directly, it may be more convenient to measure a reaction rate using another property: e.g. for reactions in which a gas is produced:

t change of volume

ra e = ------"'------

time

A is used up and its concentration falls. B is formed and its concentration increases.

Concentration D Concentration D

• ~A ~B

Time Time

• The 'gradient of the graph gives the rate of the reaction at any time.

• The steeper the gradient, the faster the rate of the reaction.

• The reaction is fastest at the start when the concentration of A is greatest.

• As the reaction proceeds, the rate slows down because the concentration of A decreases.

• When the reaction is complete, the graph levels off and the gradient becomes zero.

Activation energy

• In a gas or solution, particles are in constant motion.

• When particles collide, a reaction can only take place if tfle-..e.!.!:.ergy of the collision exceeds the activation energy of the reaction.

Enthalpy H

The activation energy of a reaction is the energy required to start a reaction by breaking bonds.

intermediate state

activation energy

reactants

ilH

products

Reaction pathway

• Activation energy is often supplied by a spark or by heating the reactants ..

• Reactions with a small activation energy often take place very readily.

• A large activation energy may 'protect' the reactants reacting at room temperature.


61

Progress check

1 Draw energy profile diagrams for the following reactions:

(a) NzD4(g)-- 2NO/g) t1H", +58 k] mol"

(b) N2(g) + 3H2(g) ------... 2NH3(g) t1H '" -92 kJ mol"

2 Write an equation to represent the enthalpy change for: (a) t1H&c (CH4)

(b) t1H&f (NOz)

3 Addition of zinc powder to 55.0 ern" of aqueous copper(lI) sulphate at 22.8 °C raised the temperature to 32.3°C. 0.3175 9 of copper were obtained.

(a) Calculate the energy released in this reaction.

(b) Write an equation, including state symbols, for this reaction.

(c) Calculate the enthalpy change for this reaction per mole of copper formed.

4 Combustion of 1 .60 g of ethanol, CzHsOH, raised the temperature of 150 9 of water from 22.0°C to 71.0ac. Find the enthalpy change of combustion of ethanol (c= 4.18 J g-' K-').

5 You are provided with data for the following reaction:

H2(g) + lig) -- 2HI(g) !J.H = +53 kJ mol"

H2(g) + 12(g) -- 2H(g) + 21(g) t1H = +183 k] mar'

(a) Draw an energy profile diagram for this reaction showing both these energy changes.

(b) Use your diagram to find out how much energy is released during bond formation in this reaction.

(c) In this reaction, what can be deduced about the relative strengths of the bonds that are broken and the bonds that are formed?

6 Use the bond enthalpy data below to find the enthalpy change for each reaction. (a) CzH/g) + 302(g) ----'--'Jo 2CO/g) + 2HzD(g)

(b) N2(g) + 3Hlg) -- 2NH/g)

bond

C-H C=O 0=0 O-H C=C C-C N=N H-H N-H

60

average bond +413 740 +497 +463 +612 +347 +945 +436 +391

enthailly. /.k mar' +

7 Use the t1H&c data below to calculate enthalpy changes for: (a) 3C(s) + 4Hig) -- C3Hs(g)

(b) C(s) + 2Hig) + 1h02(g) - CHpH(I)

substance C(s) H~(g) C~H .. (g)

CH.~OH(I) I

sir; / kJ mol' -394 -286 -2219

-72-,6"""-'--.0.1

8 Use the t1HG-f data below to calculate enthalpy changes for: (a) CzH/g) + H2(g) -- C2H6(g)

(b) SOz<g) + 2HzS(g) -- 2HzD(I). + 3S(s)

+52

-85


Rates and equilibrium

What affects a reaction rate?

The rate of a reaction may be affected by the following factors:

• the concentration of the reactants

• the surface area of solid reactants Rather than use

• a temperature change

• the presence of a catalyst.

How does reaction rate change during a reaction?

For a reaction: A ~ B,

ti t c.hange of concentration

reac IOn rare ==

time

concentration directly, it may be more convenient to measure a reaction rate using another property: e.g. for reactions in which a gas is produced:

change of volume rate = ------""---------

time

units: mol dm" 5-1.

The reaction rate can be measured as:

• the rate of decrease in concentration of A

• the rate of increase in concentration of B.

The graphs below show how the concentrations of A and B change during the course of the reaction: A - B

A is used up and its concentration falls. B is formed and its concentration increases.

Concentration 0 Concentration 0

~A ~B

Time Time

• The gradient of the graph gives the rate of the reaction at any time ..

• The steeper the gradient, the faster the rate of the reaction.

• The reaction is fastest at the start. when the concentration of A is greatest.

• As the reaction proceeds, the rate slows down because the concentration of A decreases.

• When the reaction is complete, the graph levels off and the gradient becomes zero.

Activation energy

• In a gas or solution, particles are in constant motion.

• When particles collide, a reaction can only take place if tfi(~,e~ergy of the collision exceeds the activation energy

of the reaction. ~

intermediate state

reactants

activation energy

Enthalpy H

l!.H

." products ."

The activation energy of a reaction is the energy required to start a reaction by breaking bonds,

Reaction pathway

• Activation energy is often supplied by a spark Dr by heating the reactants.

• Reactions with a small activation energy often take place very r-eadily.

• A large activation energy may 'protect' the reactants reacting at room temperature.


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