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1 a) Positive charge
b) i) 2 electrons
ii) 6 electrons
iii) 10 electrons
c) They spin in opposite directions to minimise repulsion between the pair of electrons.
2 a) Alpha particles were fired at a very thin sheet of gold foil and their subsequent path detected by a
radioactivity detector.
b) If the Plum Pudding model of the atom had been correct scientists would expect the positively charged alpha
particles to pass straight through the gold foil, but some were deflected and a few rebounded from the foil.
c) The Plum Pudding model suggested that the positive charge in an atom was spread through the atom in a
diffuse cloud of charge. To explain the results of this experiment, this was revised to propose a tiny
positively charged nucleus at the centre of the atom into which all the positive charge was concentrated.
d) Because it can be hammered into very thin gold foil (gold leaf) so the alpha particles could pass through
and not be absorbed.
3 a) The energies absorbed or emitted in electron transitions are specific fixed packets of energy, which
appear as lines on atomic spectra. This suggests that the electrons are moving between fixed energy levels.
b) Continuous bands of light energy/electromagnetic radiation
c) i) Principal quantum number of the electron shell or energy level
ii) Electron falls from n = 3 into n = 1
iii) Electron falls from n = 4 into n = 1
iv) Electrons falling back into the n = 2 quantum shell
4 a) The energy needed to remove one mole of electrons from a mole of gaseous atoms
b) log10I.E. 801 = 2.90; 2427 = 3.39; 3660 = 3.56; 25026 = 4.40; 32828 = 4.52
Graph same axes as page 12 in Advanced Chemistry for You (2nd edition)
c) The gradual rise in the first three I.E.s occurs as the second and third electrons are removed from the
same quantum shell (n = 2) but have to escape from increasingly positively charged ions. The large step
up between the 3rd and 4th I.E.s on the graph arises as the fourth electron is removed from the n = 1
quantum shell, which is much nearer to the attractive force of the positively charged nucleus.
d) i) The line gradually slopes upwards until first large step up between the 6th and 7th I.E.s, then slopes
gradually upwards again until the second large step up between the 14th and 15th I.E.s., with 16th I.E.
the highest point.
ii) The first point is the lowest with a large step up to the 2nd I.E. Then the line gradually slopes upwards
until a second large step up between the 9th and 10th I.E.s, then slopes gradually upwards again until
the third large step up between the 17th and 18th I.E.s, with 19th I.E. the highest point.
5 As shown at the bottom of page 11 in Advanced Chemistry for You (2nd edition) (without the top 4d
sub-shell).
6 a) i) 1s22s22p3
ii) 1s22s22p63s23p5
iii) 1s22s22p63s23p64s2
iv) 1s22s22p63s23p63d24s2
v) 1s22s22p63s23p63d54s1
vi) 1s22s22p63s23p63d64s2
vii) 1s22s22p63s23p63d104s1
viii) 1s22s22p63s23p63d104s24p6
b) i) Ca The sub-shells fill up from 1s to 3p then the final two electrons go into the 4s sub-shell which is
at a slightly lower energy level than the 3d sub-shell.
ii) Cr instead of the possible 3d44s2 configuration Cr adopts the 3d54s1 alternative configuration
which has the outer six electrons unpaired as this minimises the mutual repulsion between pairs of
electrons in the same orbitals.
iii) Cu instead of the possible 3d94s2 configuration Cu adopts the 3d104s1 alternative configuration
which forms a complete 3d subshell.
c) i) 1s22s22p6
ii) 1s22s22p6
Oxford University Press
protons
neutrons
electrons
a)
27
32
27
b)
47
60
47
c)
92
143
92
d)
94
148
94
e) The proportion of neutrons compared with protons increases as the atoms get larger.
f) Their stability decreases and they become more susceptible to radioactive decay.
3 a)
b)
(51.46 90) + (11.23 91) + (17.11 92) + (17.40 94) + (2.80 96)
100
4 a)
b)
c)
5 a)
4 Ionic compounds
1 Ionic; non-metal; electrons; non-metal; positively; negatively; giant; lattice; ionic; electrostatic; oppositely;
high; dissolve; molten; solid.
2 tin(ii) bromide; sodium fluoride; iron(ii) oxide; zinc chloride
The substances with giant ionic structures are made up of metal ions and non-metal ions.
3 a) Diagram of Li atom (2,1) showing electron transferred into outer shell of F atom (2,7); Li becomes Li+
(2)+, and F becomes F (2,8)
b) Diagram of two Na atoms (2,8,1) showing each one transferring an electron into outer shell of O atom
(2,6); both Nas become Na+ (2,8)+, and O becomes O2 (2,8)2
4
NO3
SO42
PO43
LiI
LiNO3
Li2SO4
Li3PO4
NH4
NH4I
NH4NO3
(NH4)2SO4
(NH4)3PO4
Ba
BaI2
Ba(NO3)2
BaSO4
Ba3(PO4)2
Cr
CrI3
Cr(NO3)3
Cr2(SO4)3
CrPO4
Li
5 a) The group number (short version of the Periodic Table in which Al is in Group 3) is equal to the positive
charge on the metal ion.
b) Short version of the Periodic Table: 8 minus the group number of the non-metal equals the charge on its
negative ion.
Long version of the Periodic Table: 18 minus the group number of the non-metal equals the charge on its
negative ion.
c) It requires too much energy for a carbon atom to either remove 4 electrons (to form C4+ ions) or to gain
4 electrons (to form C4 ions).
d) An H atom can gain 1 electron to form an H ion, gaining the electronic configuration of the noble gas
helium; or it can lose its only electron to form an H+ ion with no electrons.
6 a)
2+
Mg
or
Mg
b)
2+
Li
Br
or
Li
c)
+
2
3+
Al
or
Al
3+
Al
or
3+
Al
3+
7 a) 8
b) 8
c) CsCl
Oxford University Press
5 Covalent bonding
1 Sharing; covalent; pair; negatively; positively; four; melting; giant; simple; molecule; between; molecular;
Waals; London; temporary/instantaneous; polar; Hydrogen; hydrogen; electronegative; nitrogen/fluorine;
fluorine/nitrogen; graphite
2
F
3 a) Allotropes
b) Any fullerene/graphene
c) Diamond is very hard and does not conduct electricity whereas graphite is soft and conducts electricity.
This is explained by diamonds giant 3D network of carboncarbon bonds, with each carbon atom forming
4 covalent bonds to their nearest neighbouring atoms. On the other hand, graphites giant structure is
made up of sheets of carbon atoms arranged in hexagons, with each carbon atom forming 3 covalent
bonds to its nearest neighbours. The forces between the layers are weaker than covalent bonds, as each
carbon atom donates its fourth outer shell (2p) electron into bands of delocalised electrons located above
and below the plane of the sheets. The weaker forces between sheets make it relatively easy for layers to
slide over each other, making graphite soft (and slippery). The delocalised electrons can drift along the
layers of carbon atoms and can flow as an electric current when a voltage is applied to graphite. On the
other hand, diamond has no mobile electrons, with all its four outer shell electrons involved in its covalent
bonding, so is an electrical insulator.
4 a) Single atoms
b) van der Waals (London) forces
c) Instantaneous imbalances of electrons in atoms/molecules result in temporary dipoles that induce dipoles
on neighbouring atoms/molecules, producing relatively weak forces of attraction between atoms/
molecules.
d) As the atomic number increases (as the group is descended), the boiling point increases. This is because as
the atoms get larger and have more electrons, the opportunities for the number and size of instantaneous
dipole-induced dipole interactions increase so the forces between the atoms of the noble gases get
stronger.
5 a)
H
H
b) Dative or coordinate (covalent) bond
c)
H+
H
d) Tetrahedral
6 a) A small square
b) Trigonal (planar)
c)
O
O
d) Trigonal (planar)
7 a)
H
H
b) Its relatively low melting/boiling point
c) Graph of melting points (vertical axis) v Mr (horizontal axis, points join with line (or stick bars for each
hydride)
d) Water
e) 180184C
f) Although the permanent dipoledipole attractions decrease from hydrogen sulfide to hydrogen telluride (as
the dipole moment of the molecule decreases), the melting points rise as the molecules get larger and the
greater number of electrons means that the opportunities for the number and size of instantaneous dipoleinduced dipole interactions increase. Therefore the van der Waals (London) forces between the molecules
get stronger going from hydrogen sulfide to hydrogen telluride, outweighing the effect of the decreasing
dipole moment.
g) The presence of the relatively strong hydrogen bonds between the hydrogen and oxygen atoms in
neighbouring water molecules.
h) When the water molecules are fixed in position in ice crystals each water molecule forms two hydrogen
bonds, in an open structure which occupies a greater volume than the same mass of liquid water.
sample
being tested
3 a) Fill the bottom of a tray with balls, then add layers to sit in the holes/indentations in successive layers of
balls, leaving no gaps.
b) Make a structure in which the third row of balls are directly above the first row balls or you could make a
structure in which the first and fourth rows line up directly.
c) An aba or an abc-type structure respectively
d) Body-centred cubic structure
e) It is more open/has more space within the structure
4 a) The bonding in a giant metallic structure, in which each metal ion has donated electrons into a sea of
delocalised electrons. These mobile electrons bind the oppositely charge metal ions together.
b) Because they have donated electrons into the sea or conduction band of delocalised electrons, becoming
positively charged ions (cations).
c) They are made up of layers of ions of the same size which can slide over each other when subjected
toforces.
d) The differently sized atoms/ions disrupt the regular arrangement of the giant metallic structure, meaning
that layers cannot slide past each other as easily so the metal can withstand greater forces without
changing shape.
e) Melt the metals and stir them together; allow to cool and set to make the mixture.
f) E.g. test which is harder an alloy or pure metal by placing a tube and ball-bearing in the surface of
each; drop the same mass from the same height down the tube onto the ball-bearing; then measure
diameter of indentation made in the surface of each metal.
5 a) Na 1s22s22p63s1
Mg 1s22s22p63s2
Al 1s22s22p63s23p1
b) Na 1 electron
Mg 2 electrons
Al 3 electrons
c) Because aluminium has more electrons in the conduction band/more delocalised electrons per ion than Na
or Mg in their giant structure.
Rises to a peak in Group 4(14), then falls away rapidly to the end of the period
Increase steadily across a period to Group 7(17)
Starts high on the left of the Periodic Table and drops abruptly on the right hand side
Decreases steadily across a period
General increase across a period (with small decreases at Group 3 and Group 6)
6 a) Giant metallic and giant covalent structures found in elements in Group 1 to 4(14), followed by the simple
molecular structures of the non-metallic elements.
b) The ability to attract the electrons in a covalent bond increases as the nuclear charge increases across a
period and the size of the atoms decreases.
c) The metals with their delocalised electrons are found on the left hand side of the Periodic Table whereas
the non-metals, with their giant covalent or simple molecular structures, have no mobile electrons available
for conduction.
d) The nuclear charge increases across a period, so the electrons that enter the same shell successively are
drawn slightly closer to the nucleus and the size of the atoms decreases.
e) As the nuclear charge increases across the period, the electrons become held more strongly to the nucleus,
making it harder to remove them. (The slight fall at Group 3 is because the p sub-shell has an electron in it
which is slightly further from the nucleus than the s sub-shell. The slight fall at Group 6 is the result of
mutual repulsion between electrons in the spin pair in the outer p sub-shell.)
7 a) Rises to a peak in Group 4(14), then falls away rapidly to Group 5 and to the end of the period
b) The periods start with giant metallic structures and the giant covalent structures of Group 4(14) elements
carbon and silicon which need lots of energy to separate their particles to form a vapour. However, from
Group 5(15) onwards the elements have simple molecular structures typical of many non-metallic elements
in which relatively weak intermolecular forces can be easily overcome.
8 a) It is the 17th element in the Periodic Table which is the number of protons (its atomic number) and also
its number of electrons.
In the short version of the Periodic Table, it is in Group 7 which is the number of electrons in its outer
quantum shell.
It is in the 3rd period which equals the number of quantum shells occupied or partially occupied by its
electrons.
b) They both have outer shell configurations of s2 ..p5/same number of electrons in their outer quantum
shell (highest energy level).
9 a) Alkali metals, as when the metals react with water they form alkaline solutions of their hydroxides.
b) Lithium, as the smallest atom in the group has its outermost electron nearest to the attractive force of its
nucleus, and this electron is also shielded less from the nuclear charge than the larger atoms, so it takes
more energy to remove the outer electron to form a lithium ion. These two factors outweigh the fact that
lithium, as the smallest atom in the group, has the smallest nuclear charge attracting its outer electron.
c) rubidium + water
rubidium hydroxide + hydrogen
2Rb(s) + 2H2O(l)
2RbOH + H2(g)
d) Violent/vigorous/explosive reaction/flames (as the hydrogen released ignites)
e) Low density, soft, low melting points for metals
Na
Mg
Al
Si
Cl
Na2O
MgO
Al2O3
SiO2
P4O10
SO3/SO2
Cl2O7/
Cl2O
P4O10
SO3/SO2
Cl2O7/
Cl2O
Moles of oxygen
per mole of
element
d) Student graph
e) Formula of oxide
Moles of oxygen
per mole of
element
0.5
1.5
2.5
3/2
3.5/0.5
Li2O
BeO
B2O3
CO2
NO2
O2
OF2
0.5
1.5
0.5
f) The non-metal oxides of the third period can be oxidised to a greater extent than those in the second
period because of the presence of the 3d sub-shell which the elements can use to expand their octet,
enabling them to bond to a larger number of oxygen atoms.
4 a) The initial rise peaks at Group 2 then decreases steadily to Group 6(16) and levels off to Group 7(17).
b) The Group 1 and 2 chlorides are both high, followed by a steep fall and a levelling off at relatively low
temperatures across to the rest of period 3.
c) The ionic oxides and chlorides of Groups 1 and 2 have giant ionic structures with strong electrostatic
forces of attraction between their oppositely charged ions, operating in all directions, explaining their high
melting points. The large decrease takes place going from Group 2 to 3 in the chlorides, as aluminium
chloride exists as simple molecules, whereas aluminium oxide has a giant ionic structure and silicon dioxide
has a giant covalent structure, explaining why the steep fall occurs going from Group 4 to 5 in the oxides.
The chlorides and oxides of Group 5(15) to 7(17) are all simple molecular structures so have relatively
weak intermolecular forces, explain their low melting/boiling points.
5 a) Argon because it has the highest nuclear charge in Period 3 whilst all Period 3 atoms are filling the same
energy level/shell with electrons.
b) The metal atoms lose electrons that can result in the loss of their outer shell so the positive ions are
smaller than the original atoms. The non-metal atoms gain one or more electrons into their outer shell,
increasing the mutual repulsion between electrons in that shell so increase in size.
c) Silicon (because it takes too much energy to either gain 4 electrons or lose 4 electrons) and argon (because
it has a complete outer octet of electrons which is a very stable electronic configuration).
6 a)
b)
c)
d)
e)
7 a) The first two chlorides dissolve in water whereas the remaining chlorides react, being hydrolysed by water,
forming white fumes of hydrogen chloride gas and leaving acidic solutions.
b) The chlorides of sodium and magnesium are purely ionic and dissolve in water, resulting in solutions of pH
7 and 6.5 respectively. Then from aluminium chloride, with some covalent character in its bonding and a
simple molecular structure, onwards the chlorides are hydrolysed by water.
c) The high charge density on the Al3+ ion weakens the bonds in the water molecules surrounding the
hydrated ion. When an O H bond breaks in a water molecule it releases an H+(aq) ion into solution,
making the solution acidic.
d) SiCl4 has empty 3d orbital into which water molecules can donate pairs of electrons and initiate attack,
resulting in the hydrolysis of silicon chloride. There is no equivalent 2d orbital in the carbon atom of CCl4
so no attack occurs with water, and two immiscible layers form.
At
3 a) Sodium bromide
b) Ag+(aq) + Br(aq)
AgBr(s) or Ag+Br(s)
c) Photographic film, as silver bromide decomposes in light to form grey deposits of silver metal.
4 a) NaCl(s) + H2SO4(l)
b)
NaHSO4(s) + HCl(g)
hydrogen
chloride
gas
sodium
chloride +
conc. H2SO4
+ 2Li
2Li + F2
2Li+ + 2e
11 d-block elements
1 Reactive; coloured; oxidation; Complex; ligands; catalysts
2 Any four transition metals and their uses, with relevant properties described.
3 a) i) 1s22s22p63s23p63d34s2
ii) 1s22s22p63s23p63d74s2
iii) 1s22s22p63s23p63d104s2
b) V and Co form ions with a partially filled d orbital in their electronic configuration whereas Zn does not
(the Zn2+ ion has a complete 3d sub-shell).
c) A d-block element
4 a) 1s22s22p63s23p63d54s1
b) 1s22s22p63s23p63d104s1
c) The chromium atom has a half-filled 3d sub-shell which minimises the mutual repulsion between electrons
in orbitals compared with a configuration of [Ar]3d44s2. Copper adopts the configuration that completes
its 3d sub-shell.
5 a) Fe2+ 4 out of the 5 boxes for the 3d orbitals will each be occupied by 1 electron, with the other box
contains 2 electrons.
Fe3+ The 5 boxes for the 3d orbitals will be occupied by 1 electron.
b) Cu+ The 5 boxes for the 3d orbitals will each be occupied by 2 electrons.
Cu2+ 4 out of the 5 boxes for the 3d orbitals will be occupied by 2 electrons, with 1 box containing a
single electron.
c) Mn2+ The 5 boxes for the 3d orbitals will each be occupied by 1 electron.
Mn4+ 3 out of the 5 boxes for the 3d orbitals will be occupied by 1 electron.
d) Fe3+ is more stable than Fe2+, as the 3+ ion has the half-filled 3d sub-shell, with less mutual repulsion
between electrons.
Cu+ is more stable than Cu2+, as the 1+ ion has the complete 3d sub-shell, with its symmetrical
distribution of charge around the nucleus, giving it added stability.
6 a) Because chromium has 6 electrons available to get involved in bonding 1 4s electron and 5 3d electrons.
b) The energy involved in removing 6 electrons would be too high for an energetically stable compound to be
formed containing Cr6+ ions.
c) Chromate(vi) ions, CrO42, and dichromate(vi) ions, Cr2O72
7 a) Manganese, +7
b) Zinc
c) Iron
d) Chromium and manganese
e) Copper
f) Copper
g) Vanadium
h) Chromium
i) Cobalt
j) Iron
k) Copper
l) Nickel
8 a) They donate one (or more) lone pair of electrons into empty orbitals on the central metal ion, forming
dative (coordinate) covalent bonds.
b) 4
c) Tetrahedral
d) Because the complex carries a negative charge
e) E.g.
H
H
H
2+
H
H
Co2+
H
O
O
H
H
H
H
pink
This complex is cationic.
f) Linear
g) It helps distinguish between the similarly coloured silver halide precipitates formed in positive tests for
halide ions.
h) The two ligands at the points of the octahedron are further from the central transition metal ion than the
4 ligands in the same plane as the metal ion.
i) i) 3+ii)
2+iii)
3+
9 a) It forms only one coordinate (dative) covalent bond (or donates only one lone pair of electrons) to the
central transition metal ion in a complex.
b) E.g.
H2
3+
C
H
H2C
H H
N
H
H
N
N
CH2
H
Cr 3+
H
CH2
N
N
H
N
H H
H2C
C
H
H2 H
c) i)
6ii)
hexadentateiii)
2
Fe3+ + 3e
10 a) Fe
2+
b) Cu + e
Cu+
2+
3+
c) V
V + e
+
d) 2H + VO2+ + e
V3+ + H2O
e) 4H+ + VO2+ + 3e
V2+ + 2H2O
2+
+
f) 2H2O + Mn
4H + MnO2 + 2e
or
4OH + Mn2+
2H2O + MnO2 + 2e
g) 6H+ + CrO3 + 4e
Cr2+ + 3H2O
+
h) H2O + MnO3
2H + MnO4 + e
or
2OH + MnO3
H2O + MnO4 + e
i) 14H+ + Mn2O7 + 10e
2Mn2+ + 7H2O
j) Reactions in b), d), e), g) and i) are reduction reactions because the reactant is gaining electrons, and there
is a decrease in their oxidation state.
k) Fe (in a)), V2+ (in c)), Mn2+ (in f)) and MnO3 (in h)) are acting as reducing agents as they all donate
electrons (increase their oxidation state), and become oxidised themselves.
l) V2+ + VO2+ + 2H+
2V3+ + H2O
2+
2+
m) 2Cu + Mn + 2H2O
2Cu+ + MnO2 + 4H+
11 a)
b)
Homogeneous catalysis the reactants and the catalyst are in the same phase.
Heterogeneous catalysis the reactants and the catalyst are in different phases.
Homogeneous catalysis: 2+
Fe (aq)
e.g. 2I(aq) + S2O82(aq)
I2(aq) + 2SO42(aq)
Heterogeneous catalysis:
MnO2(s)
e.g. 2H2O2(aq)
2H2O(l) + O2(g)
c) It can help form transition intermediates by redox reactions with reactants (see enthalpy level diagram on
page 155 in Advanced Chemistry for You (2nd edition)).
d) E.g. Fe in Haber process in manufacture of ammonia, V2O5 in Contact process in manufacture of sulfuric
acid, Ni in hydrogenation of oils in manufacture of margarine, Pt/Rh in manufacture of nitric acid.
12 a) Fe2+
Fe3+ + e
b) 8H+ + MnO4 + 5e
Mn2+ + 4H2O
2+
+
c) 5Fe + 8H + MnO4
5Fe3+ + Mn2+ + 4H2O
2+
2+
NH3
H3N
Cu2+
H3N
OH2
H2O
2+
Ni2+
NC
Cl
H
N
H
H
H
C
H
H
H
or
C
H
H
d) chloroethane, CH3CH2Cl, and
H
e) ethanamide, CH3CONH2, and
H
H
Cl
O
C
N
H
f) ethanoic acid, CH3COOH, and
H
H
C
H
H
H
O
C
O
3 C3H6
4 a) CnH(2n + 2)
b) C11H24
5 a)
H
b)
H
H
O
O
C
H
c)
H
H
d)
H
e)
H
f)
H
g)
H
Br
Br
h)
O
H
N
H
O
C
O
Cl
Cl
i)
H H
j)
F
O
C
O
6 a) 2-Chloropropane
b) Propanal
c) Methanoic acid
d) 4-Chloro-2,2-difluoropentane
7 a)
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
b)
Cl
c)
Br
Br
Br H
Br
Br
Cl H
Cl
H
H
Br H
Br
H
H
H
H
Br
H
H
H
H
Br
H
H
Br H
Br
H
H
H
H
H
H
H
H
H
H
Br
Br
Cl H
H C
Br
H
H
8 a), b) and d) See answers on page 451 of Advanced Chemistry for You (2nd edition)
c)
H H
H
H
H
H
9 a) i)
and
H
C
Br
H
CH3
C
H
H3C
Z-but-2-ene
Br
E -1-bromo-2-fluoroethene
CH3
Z-1-bromo-2-fluoroethene
H
C
F
ii) H3C
C
H
E -but-2-ene
b) i) CHBrClF because it contains a carbon atom bonded to four different groups/atoms (contains an
asymmetric carbon atom or a chiral centre).
ii)
H
H
C
I
Br
C
Cl
Cl
I
Br
13 The alkanes
1 Saturated; C2H6; hexane; combustion; water; hydrogen; sunlight (U.V. light); incomplete; carbon; monoxide;
sulfur; nitrogen; acid
2 a) CnH(2n + 2)
b) C12H26
c)
H
H
H
H
H
d) No, CnH2n
e) The bond angles between carbon atoms in cyclobutane are about 90 (under strain), as they are much less
than the 109.5 tetrahedral angles between the carbon atoms in butane (which minimise repulsion
between bonding pairs of electrons).
3 a) Fractional distillation
b) Petroleum gases; petrol/gasoline; kerosene; diesel; lubricating oil; fuel oil; bitumen
c) The larger alkanes have stronger intermolecular forces/van de Waals forces between their molecules (as
they contain more electrons within each molecule, therefore giving rise to more instantaneous dipoles and
hence more induced dipoles on their neighbouring molecules, producing stronger forces of attraction
between molecules).
4 a)
ice/water mixture
(to condense water vapour)
to water pump
(to draw gases
through the
apparatus)
deposits of
soot (carbon)
hexane
sand tray
(for safety)
limewater
turns milky
(showing CO2
is produced)
14 The alkenes
1 double; reactive; high; double/pi; electrophiles; electrophilic; Bromine; colourless; addition
2 a) H
H
C
Cl
C
Cl
Cl
Cl
H
b) E/Z (cistrans/geometric) isomerism
c) There is no free rotation about the double bond in 1,2-dichloroethene.
d) Cl
Cl
Cl
H
C
F
C
H
C
Cl
3 a) All three could produce carbon dioxide and water as combustion products but heptane would burn with the
cleanest flame.
b) Hept-1-ene and cycloheptene would decolourise the bromine water, but heptane would not react with it.
4 a) C2H4
b) Decane, octane and ethene
c) Cracking
d) It converts larger, less useful alkanes into smaller, more useful alkanes.
5 a) CH3CH2CH3
b) Propene, hydrogen, propane
c) Nickel
d) Finely divided to give a large surface area
e) 140C
f) It straightens the hydrocarbon chains in the oil molecules so they can pack together more effectively,
increasing intermolecular (van der Waals) forces between molecules which increase the melting point of
the product compared with the oil, thus making the margarine a spreadable solid.
6 a)
b)
c)
d)
e)
f)
g)
7 a) C2H4Br2
b) C2H5Cl
c) CH2FCHFCHFCH2F
d) CH3CHBrCH3
8 a) (CH3)3C+ > CH3C+HCH3 > CH3C+H2
b) The tertiary carbocation has three alkyl groups donating electrons to its positively charged carbon atom,
reducing the charge density and in effect spreading the positive charge around the whole ion, making it
more stable. The secondary carbocation has one fewer alkyl groups and the primary has only one alkyl
group exerting the inductive effect.
H
H
b)
H
H
Br Br
H H H
Cl H H
c)
Cl
Cl H H
F Br Br H
d)
F
16 The alcohols
1 methanol; higher, hydrogen; hydrogen; sodium; ester; catalyse; aldehyde; carboxylic; ketones; Tertiary;
nucleophilic; catalyst; dehydration/elimination; alkene
2 a) i)
H
ii)
iii)
O
H
17 Aromatic compounds
1 benzene; hexagonal; delocalised/six; plane; pi; electrophilic
2 a) Carbon dioxide and water
b) C6H6 + 7.5O2
6CO2 + 3H2O
or 2C6H6 + 15O2
12CO2 + 6H2O
c) Smoky / dirty
3 a)
H
or
C
C
C
C
H
b) Each of the six carbon atoms in the hexagonal ring forms 3 single/sigma bonds, to two other carbon
atoms and a hydrogen atom. This leaves each carbon atom with 1 electron in a p atomic orbital. The
lobes of these p orbitals overlap above and below the plane of the other atoms, and the 6 electrons
become delocalised around the benzene ring.
c)
enthalpy
C6H6 + 3H2
208 kJ mol1
C6H12
d) 360kJmol1
e)
enthalpy
+ 3H2
+ 3H2
360 kJ mol1
208 kJ mol1
C6H12
f) Higher
g) 152kJmol1
4 a) C6H5NO2 + H2O
b) Nitration
c) Nitronium ion/nitryl cation, NO2+; reflux benzene and the nitrating mixture of concentrated nitric and
concentrated sulfuric acids, not above 50C.
d) HNO3 + 2H2SO4
NO2+ + 2HSO4 + H3O+
5 a) C6H5Cl + HCl
b) One of the Cl atoms in the Cl2 molecule donates a pair of electrons into the empty p orbital on the Al
atom in AlCl3. This draws electrons away from the other Cl atom, giving it a partial positive charge.
(Alternatively, the bond between the 2 Cl atoms in Cl2 which breaks heterolytically, forming a Cl+ ion.)
This electron-deficient Cl acts as an electrophile attacking the benzene ring, forming a positively charged
intermediate and leaving an [AlCl4] ion. The AlCl3 is regenerated when the benzene rings delocalised
pi-bonding system is re-established by releasing an H+ ion which accepts a pair of electrons from an
Cl in the [AlCl4] ion.
6 a) C6H5CH2CH3
b) The HCl reacts with C2H4 in an addition reaction to form C2H5Cl.
Then:
H
+
CH3 C Cl
AlCl3
CH3CH2 +
AlCl4
carbocation
H
+
CH2CH3
AlCl4
CH2CH3
+
CH2CH3
AlCl4
CH2CH3
+
HCl
AlCl3
O
H
C
H
b)
H
H
c)
H
O
C
H
NO2
NO2
CH3CH2
C
NH
NO2 + H2O
H
5 a) CH3CH2COOH
b) CH3CH(OH)CH3
c) CH3CH2C(CN)(OH)CH2CH3
d) CH3CH2CH2HC NOH
Oxford University Press
CH3COONa+ + CH3CH2OH
ethyl ethanoate
+
sodium hydroxide solution
heat
(electric
heating
mantle
could also
be used as
alternative
heat source)
c) RCOOCH2
CH2OH
RCOOCH + 3NaOH
RCOOCH2
6 a) CH3CH2COOH
b) CH3CH2COOH + H2O CH3CH2COO + H3O+
c)
O H O
CH3CH2C
CCH2CH3
O H
O
+
d) Propanoic loses an H ion from its COOH group more easily than propan-1-ol loses an H+ ion from its
OH group. This is because the presence of the extra O atom pulls electrons away from the O H bond
in the COOH group, weakening it.
Also, of the anions formed when an H+ ion is lost, the propanoate ion is less likely to attract H+ ions
to act as a base and re-form the undissociated molecule, as the delocalisation of electrons around
the COO group means that its negative charge is spread over all three atoms (and not concentrated on
the end O atom as it is in the propoxide ion, CH3CH2CO).
H
*C
COOH
CH3
21 Polymers
1 polymers; monomers; poly(ethene); addition; condensation; any addition polymer, e.g. poly(ethene)/
poly(propene)/polystyrene/poly(phenylethene)/poly(chloroethene)/poly(tetrafluoroethene); any condensation
polymer, e.g. nylon, polyester, polyamide, Kevlar, poly(lactic acid), DNA; Thermoplastics/Thermosoftening
plastics; thermosets/thermosetting plastics; degradable; recycled
2 a) In a blocked cylinder of ethene
b) Its polymer chains were highly branched and could not pack closely together.
c) HDPE is made of straighter chain polymers than LDPE so its molecules can pack together more closely,
resulting in stronger van der Waals forces.
d) It is more rigid and has a higher softening temperature (so can be sterilised with boiling water).
e) An impurity in a reaction vessel proved to be an essential component of the catalyst used.
f) LDPE e.g. plastic bags, toys
HDPE e.g. babys bottles, water pipes
3 a) temporary/instantaneous dipole-induced dipole interactions, resulting in van der Waals/London forces
b) hydrogen bonds (and van der Waals/London forces)
c)
H H
H
O H H
H
C
H O
H
H H O
H
d) Cross-links
e) C
f) C will be hard and rigid. B will have a greater tensile strength than A.
4 a) (C2H4)n
b) Addition polymerisation
c)
H H H H H
C
H
C
H H H H H H
d) Poly(propene)
Isotactic because all the methyl groups are on the same side of the chain
e) H2C CHCH3
f) E.g. carpets, trawler nets, milk bottle crates
5 a) The reaction is started by a peroxide free radical initiator which reacts with ethene, breaking the double
bond homolytically. A chain reaction follows as the alkyl free radicals bond with ethene molecules
increasing the length of the free radical until a termination step occurs when two free radicals react
together to complete a polymer chain.
b) M CH2 CH3
M CH2 CH2 CH2 CH3
M CH2 CH2 CH2 CH2 CH2 CH3
Ziegler catalyst
CH2
CH2
CH2
CH2
6 a)
H H H H O
H H H H H H H
b) HOOCCH2CH2CH2CH2COOH or ClOCCH2CH2CH2CH2COCl and H2NCH2CH2CH2CH2CH2CH2NH2
c) Water with the di-carboxylic acid or hydrogen chloride with the di-acyl chloride
d Condensation (or addition-elimination)
e) Amide link
f) Proteins
7 a) H2NCH2CH2CH2CH2CH2CH2NH2 and HOOCCH2CH2CH2CH2CH2CH2CH2CH2COOH or
ClOCCH2CH2CH2CH2CH2CH2CH2CH2COCl
b)
O H H H H H H H H
H H H H H H H
C
CH2
CH2
O
d) Permanent dipoledipole forces (and temporary/instantaneous dipole-induced dipole van der Waals/
London forces)
e) Drawing out the polymer from a narrow jet to strengthen the intermolecular forces as the chains align
f) A thermosetting plastic (as a cross-link could form when two central OH groups from propane1,2,3-triol in repeating units of the adjacent polyester chains can react with a dicarboxylic acid monomer,
joining the two chains together this could happen at any points along the chains, forming a network of
cross-links).
g) It would be more rigid and heat resistant than Terylene.
9 a)
H
C
H H
b) Poly(phenylethene) (or polystyrene)
c) Addition
d) If the bulky benzene rings are all aligned on the same side or arranged randomly, the polymer chains could
be bent/curved compared with the straight chain with the benzene rings alternating regularly on one side
then the other. The straighter chains could pack together more tightly, giving this plastic a higher density
and a higher softening temperature.
10
22 Organic synthesis
1 a) E.g. add concentrated hydrogen bromide to the ethene to form bromoethane.
b) E.g. add concentrated hydrochloric acid to the ethene to form chloroethane. Then add excess ammonia
solution to the chloroethane to form ethylamine.
c) E.g. add steam in presence of conc. phosphoric acid catalyst to make ethanol. Then oxidise the ethanol
with acidified (dil. sulfuric acid +) potassium dichromate solution dropwise, warm and distil off the ethanal
formed.
d) E.g. add steam in presence of conc. phosphoric acid catalyst to make ethanol. Then completely oxidise
the ethanol by refluxing with excess acidified (dil. sulfuric acid +) potassium dichromate solution to make
ethanoic acid. Add phosphorus(v) chloride to convert to ethanoyl chloride.
e) E.g. add steam in presence of conc. phosphoric acid catalyst to make ethanol. Then completely oxidise
the ethanol by refluxing with excess acidified (dil. sulfuric acid +) potassium dichromate solution to make
ethanoic acid. Add phosphorus(v) chloride to convert to ethanoyl chloride, followed by addition of
ammonia solution to make ethanamide.
f) E.g. add concentrated hydrogen bromide to the ethene to form bromoethane. Then boil bromoethane
under reflux with potassium cyanide dissolved in ethanol to form propanenitrile. Then hydrolyse the
propanenitrile by boiling/heating under reflux with hydrochloric acid, to form ethanoic acid. This can then
be reduced by lithium hydridoaluminate(iii)/LiAlH4 in dry ether, followed by water to form ethanol in order
to make propan-1-ol.
g) E.g. add steam in presence of conc. phosphoric acid catalyst to make ethanol. Then completely oxidise
the ethanol by refluxing with excess acidified (dil. sulfuric acid +) potassium dichromate solution to make
ethanoic acid. Add phosphorus(v) chloride to convert to ethanoyl chloride, followed by addition of conc.
ammonia solution to make ethanamide. Finally, add bromine and concentrated sodium hydroxide solution
to remove a carbon atom and obtain methylamine.
2 a) A = sodium ethanoate, CH3COONa+
B = ethanoyl chloride, CH3COCl
C = ethanamide, CH3CONH2
D = ethanoic acid, CH3COOH
E = ethanol, CH3CH2OH
F = ethyl ethanoate, CH3COOCH2CH3
b) Ethyl ethanoate
c) Hydrolysis
d) i) Dehydration / elimination
ii) Reduction / redox
3 1 = Reflux with red phosphorus and iodine/phosphorus(iii) iodide
2 = boil/reflux with hydrochloric acid
3 = sodium hydroxide solution
4 See answer on page 451 in Advanced Chemistry for You (2nd edition).
11
23 Organic analysis
1 empirical; mass; relative; molecular; molecular; mass; radiation/waves; visible; compared; database;
finger-printing
For answers to Q2 and 3 see page 451 in Advanced Chemistry for You (2nd edition).
4 a) CH3COCH2CH3
b) [CH3COCH2CH3]
c) It enables us to work out the molecular formula.
d) The masses measured to a greater degree of accuracy for each atom mean that there are small, but
detectable, differences in the relative molecular masses of different compounds that are unique to that
compound (and any isomers of the compound).
e) i) [CH3CO]+
ii) [CH3COCH2]+
iii) [CH3CH2]+
f) Peaks at m/z values of 72 and e.g. 14, 17, 27, 45, 55, 58
5 a) CnH(2n + 2)
b) 114
c) C8H18, with regularly-spaced peaks as the hydrocarbon chain fragments producing ions with different
numbers of CH2 units
6 a) Violet/indigo as the low end of the visible spectrum (red, orange, yellow and blue) is all absorbed by
the compound
b) The absorption bands are too broad for accurate finger-printing/not all organic compounds absorb
energy in this range of the electromagnetic spectrum
7 a) Each organic compound has many characteristic peaks that can be used to finger-print compounds/each
compound has a unique IR spectrum.
b) They absorb energy/radiation that corresponds to the resonance frequency of their bonds which causes
the bonds to vibrate at their characteristic frequencies
c) X = O H
Y = C H
d) IR spectra are most useful for determining the bonds/functional groups present so you need a combination
of analytical techniques to be sure of the actual structure of a new compound.
8 a) A = CH3OCH3
B = CH3CH2OH
b) In A we have peaks caused by [CH3]+ at 15, [CH3O]+ at 31, and [CH3OCH2]+ at 45, as well as the
molecular ion at 46.
In B we have peaks caused by [CH3]+ at 15, [CH3CH2]+ at 29, and [CH3CH2O]+ at 45, as well as the
molecular ion at 46.
c) In A all the H atoms/protons are equivalent so there is only one peak whereas in B there is a peak for
the CH3, the CH2 and the OH H atoms/protons.
d) The relative numbers of the H atoms/protons in different molecular/chemical environments.
e) The first ( OH) peak at chemical shift 5p.p.m. would be a singlet, the next ( CH2) peak a quartet,
and the largest peak ( CH3) would be a triplet.
12
24 Enthalpy changes
1 exothermic; rises/increases; less; endothermic; fall/decrease; positive; 298; 100/101; combustion; change;
oxygen; standard
2 a) NaOH(aq) + HCl(aq)
NaCl(aq) + H2O(l)
For answers to Q2 b), c) and d) see page 451 in Advanced Chemistry for You (2nd edition).
e)
data
logger
temperature
probe
temp
/C
thermometer
lid
lid
time /s
polystyrene beaker
polystyrene beaker
f) Measurement uncertainty associated with volume of solutions (if volumes are measured out are actually
lower than 100cm3, the value calculated for enthalpy change will be too low and vice versa) and
temperature change (if temperature change measurement is too high the value calculated for enthalpy
change will be too high and vice versa). There is also the error in the temperature readings due to energy
losses to the surroundings (this will produce a value that is too low; although the temperature change error
can be adjusted using a graph as shown on page 317).
3 a)
thermometer
thermometer
to water
pump
stirrer
water
water
copper
calorimeter
alcohol
block of
wood
fuel
For answers to Q3 b), c) and d) see page 451 in Advanced Chemistry for You (2nd edition).
e) Energy losses to the surroundings, as not all the energy from the burning fuel will be transferred to the
water in the calorimeter (plus some incomplete combustion).
4 a) Enthalpy of atomisation of nitrogen
b) Enthalpy of combustion of propane
c) Enthalpy of formation of propane
3C + 4H2 (+5O2)
enthalpy
C3H8 (+5O2)
3CO2 + 4H2O
reaction pathway
enthalpy
C(graphite) + O2
395.4 kJ mol1
393.5 kJ mol1
CO2
reaction pathway
c) As graphite has the lower enthalpy value of the two allotropes, it is chosen as the standard form of the
element carbon and given an enthalpy value of zero.
For Q7 and Q8 see page 451 in Advanced Chemistry for You (2nd edition).
9 a) See page 451 in Advanced Chemistry for You (2nd edition).
b) The bond enthalpy values are average values from a range of molecular environments so calculating an
enthalpy change for a specific reaction will only provide an approximate answer (and calculation is only
valid if all substances are in their gaseous state).
25 Lattice enthalpy
1 change; one; gaseous; ionic; negative; Haber; standard; Cl(g); NaCl(s)/Na+Cl(s); Na(s); Cl2(g); H3; H2,
formation; atomisation; ionisation; atomisation; affinity
2 a) Li+(g) + F(g)
b)
Li + (g) + F (g)
LiF(s)/Li+F(s)
Hlattice
H2
K + Br (s)
H3
Li(s) + F2(g)
c)
d)
T C
(T + 10) C
activation
energy
Ea
energy
At the higher temperature the reacting particles have more energy and will move around faster, resulting
in more frequent collisions but, more importantly, there will also be a much higher proportion of those
collisions with energy greater than the activation energy, i.e. a much higher rate of successful/effective
collisions (as shown by the area under the curve increasing at the higher temperature on the
MaxwellBoltzmann distribution).
b)
number
of particles
new Ea
Ea
with catalyst
energy
Using a catalyst lowers the activation energy, meaning that more of the collisions in any given time
between reacting particles result in a reaction/are successful/effective (as shown by the area under
the curve increasing when the value of Ea is decreased on the MaxwellBoltzmann distribution).
Hence the rate of reaction increases with a catalyst.
c) Homogeneous catalysis occurs in a reaction in which the reactants and the catalyst are in the same state
or phase.
Fe2+(aq)
2
e.g. 2I (aq) + S2O8 (aq)
I2(aq) + 2SO42(aq)
Heterogeneous catalysis occurs in a reaction in which the reactants and the catalyst are in different states
or phases.
MnO2(s)
e.g. 2H2O2(aq)
2H2O(l) + O2(g)
Oxford University Press
5 a) E.g. iron/iron(iii) oxide to make ammonia; vanadium(v) oxide to make sulfuric acid/sulfur trioxide/sulfur(vi)
oxide; Pt/Rh to make nitric acid
b) The hydrogenation straightens the hydrocarbon chains in the oils, enabling them to pack together more
closely with stronger van der Waals (London) forces, increasing the melting point of the oil and turning it
into a spreadable solid.
c) They enable carbon monoxide and nitrogen oxides to react together on their honeycomb structure in the
exhaust system of a vehicle, the carbon monoxide being oxidised to carbon dioxide and the nitrogen
oxides being reduced to nitrogen.
d) They convert carbon monoxide to the greenhouse gas carbon dioxide/do not remove carbon dioxide from
exhaust gases.
6 a) Proteins that act as biological catalysts.
b) E.g. catalase breaking down toxic hydrogen peroxide in the liver
c) The shape of their active site changes so substrate molecules can no longer bind to it and react.
d) Fermentation
e) C6H12O6(aq)
2C2H5OH(aq) + 2CO2(g)
7 a) Diagram of magnesium and sulfuric acid in a conical flask attached to a gas syringe/inverted measuring
cylinder with gas collecting over water
b) Hydrogen; a lighted splint will produce a squeaky pop
c) Mg(s) + H2SO4(aq)
MgSO4(aq) + H2(g)
d) Student graph, filling more than half the area of the graph paper, axes fully labelled, sensible scale chosen,
points plotted accurately, smooth curve through points.
e) Steeper curve, levelling off at 80cm3
f) The smaller pieces have the larger surface area, so more magnesium atoms are exposed to attack by the
H+(aq) ions, resulting in more frequent collisions between them and a faster rate of reaction.
g) Lower the temperature; use less concentrated acid; use a lump of magnesium with less surface area than
the ribbon
h) About 1.0cm3s1 (+ or 0.1cm3s1)
28 Rate equations
1 concentration; experiments; rate; k; varies; higher; increase; powers; 3; first/1st; second/2nd; zero;
mechanism; slowest; determining; determining equation
2 a) The rate constant; mol2dm6s1
b)d) See page 452 in Advanced Chemistry for You (2nd edition).
e) i)
rate
[Y]
ii)
rate
[Z]
3 a) Student graph, filling more than half the area of the graph paper, axes fully labelled (with Initial rate/
moldm3s1 up the vertical (y) axis and concentration N2O5/moldm3 along the horizontal (x) axis),
sensible scale chosen, points plotted accurately, straight line through points.
b) As the concentration of N2O5 doubles, the reaction rate doubles.
c), d) See page 452 in Advanced Chemistry for You (2nd edition).
e) Substitute the values from one of the experiments to determine the initial rate into the rate equation.
f) and g) See page 452 in Advanced Chemistry for You (2nd edition).
h)
[N2O5]
/ 103 mol dm3
time
i) The decay curve will have a constant half-life./The time for the [N2O5] to fall to half its value will be
constant.
4 a) The brownish colour of the iodine will fade as the reaction proceeds.
b) i) 1, 2 and 3
ii) 1, 6 and 7
iii) 1, 4 and 5
c), d) (Changing the concentration of iodine has no effect on the rate) and e) See page 452 in Advanced
Chemistry for You (2nd edition).
f) No, because iodine must only be involved in fast steps in the mechanism of the reaction as it is zero order
with respect to iodine
g) See page 452 in Advanced Chemistry for You (2nd edition).
5 a) As the volume of the reacting mixture changes, the level of the liquid in the narrow-bore glass tube
changes and can be measured on the scale next to the tube as time passes.
b) See page 452 in Advanced Chemistry for You (2nd edition).
6 a) and b) See page 452 in Advanced Chemistry for You (2nd edition).
c) Colorimeter, as the bromine formed causes the solution to become orange/yellow
or measure change in conductivity over time as the number of ions in solution decreases as the reaction
proceeds
or titration, e.g. quenching reaction ,then finding concentration of acid at different times
7 a) The C Br bond in RBr breaks heterolytically, with Br taking both electrons to form a Br ion, and
leaving a positively charged tertiary carbocation. This carbocation is immediately attacked by an OH ion
to form the alcohol ROH.
b) The C Br bond in RBr starts breaking as the OH ion starts forming a bond by donating a pair of
electrons to the partially positively charged C atom in RBr. This forms an intermediate in which the
C Br bond breaks and the C O bond forms to make the alcohol ROH.
c) See page 452 in Advanced Chemistry for You (2nd edition).
d) The rate equation would be 1st order with respect to 2-methyl-2-bromopropane (a tertiary
halogenoalkane), i.e. as we double its concentration the rate of reaction doubles. The formation of the
carbocation from 2-methyl-2-bromopropane is the rate determining (slowest) step in the reaction
mechanism. However, it would be zero order with respect to the hydroxide ions, as the hydroxide ions
are involved in the fast step, attacking the carbocation rapidly as soon as it is formed.
29 Equilibrium mixtures
1 reversible; products; equilibrium; product; constant; forward/reverse; reverse/forward; dynamic; position;
change; catalyst; established/achieved/reached; position
2 a)
b)
c)
d)
Shift to the left/reactants, as this produces fewer moles/molecules of gas and will reduce the pressure
Shift to the left/reactants, as this will reduced the concentration of hydrogen
Shift to the right/products, as this will lower the temperature as the forward reaction is endothermic
No effect on the position of equilibrium
3 a) Solution will turn orange as more dichromate(vi) ions are formed because the position of equilibrium shifts
to the right to remove H+(aq) ions.
b) Solution will turn yellow as more chromate(vi) ions are formed because the position of equilibrium shifts
to the left to replace H+(aq) ions lost when they react with the OH(aq) ions added, forming water.
4 a) The amount of solid increases as more PCl5 is formed in order to reduce the pressure of the system
b) The enthalpy change of the forward reaction is endothermic as the position of equilibrium has shifted
to the right when the temperature was increased.
5 a)
b)
c)
d)
e)
f)
1 mole
?
NH4NO3
1 mole
2400 tonnes
2400000000
=
(4 1.0) + (2 14.0) + (3 16.0) moles
=
2400000000
80
moles
(2400000000
) (14.0 + 3.0)g
80
= 510000000g = 510 tonnes
and
2400000000
mass of nitric acid needed =
[(1.0 + 14.0 + (3 16.0)]g
80
30 Equilibrium constants
1 constant; [G]c; [E]a; [F]b; gases; pressures; py(Z); ps(T); products; equilibrium; composition; Kc; position;
Kc; Kp; constant; decreased; catalyst; constant; unchanged/not affected
[Fe(SCN)]2+
[Fe3+] [SCN]
b) See page 452 in Advanced Chemistry for You (2nd edition).
c) It lies well over to the right hand side/products.
2 a) Kc =
2(NO)
p
p(N2) p(O2)
p2(NO2)
b) Kp =
p(N2O4)
p2(HBr)
c) Kp =
p(H2) p(Br2)
d) See page 452 in Advanced Chemistry for You (2nd edition).
3 a) Kp =
5 a) Kp =
[HI]2
[H2] [I2]
b) As there are the same number of moles of reactants and products so the units in the equilibrium
expression cancel out completely.
c) and d) See page 452 in Advanced Chemistry for You (2nd edition).
6 a) Kc =
31 Acid/base equilibria
1 hydrogen/H+; accept; conjugate; conjugate; Cl; strong; dissociate/ionise; dissociation/equilibrium; weaker;
concentration; log[H+(aq)]; indicator; titration; buffer; weak; salts; alkali
2 a)
Test
Turns red
Stays blue
Sodium carbonate
No reaction
Magnesium ribbon
No reaction
b) Water enables ethanoic acid to display its acidic properties because it acts as a base, accepting an H+ ion
from the carboxylic acid group/ COOH, so a small proportion of ethanoic acid molecules dissociate,
forming ethanoate ions/CH3COO(aq) and H3O+(aq)/H+(aq) ions.
c) Any test, e.g. add sodium hydrogencarbonate/universal indicator/pH meter/pH sensor (probe)
For questions 3 and 4 see answers on page 463 in Advanced Chemistry for You (2nd edition).
5 a) A small percentage of water molecules dissociate, according to the reaction: H2O(l) H+(aq) + OH(aq)
As Kw of water is 1.0 1014, = [H+(aq)] [OH(aq)], the concentration of the H+(aq) ions
must be 1.0 107 moldm3.
Therefore the pH of water at 25C is log(1.0 107) = 7.0
b) In water the concentration of the OH(aq) is also 1.0 107moldm-3.
The ionic product is the equilibrium constant for water given by the expression:
Kw = [H+(aq)] [OH(aq)]
= (1.0 107moldm3) (1.0 107moldm-3)
= 1.0 1014mol2dm3
c) See answers on page 452 in Advanced Chemistry for You (2nd edition).
6 a) The expression for the equilibrium constant when an acid is added to/dissolves in water. For example:
HCN(aq) H+(aq) + CN(aq)
Giving the acid dissociation constant, Ka:
[H+(aq)] [CNaq)]
[HCN]
b) Hydrocyanic acid/HCN because it has the smallest dissociation constant (so has the least proportion of
its molecules dissociated in aqueous solution)
c) See answers on page 452 in Advanced Chemistry for You (2nd edition).
7 a) b)
pH
pH
volume of base
added / cm3
volume of base
added / cm3
c) d)
14
pH
pH
volume of base
added / cm3
volume of base
added / cm3
e) It is the pH of a solution where there is an equal balance of an indicators coloured species in a solution
i.e. the point where it changes colour (although this appears to occur over a range of pH values).
f) pKInd gives us the pH at which an indicator has its equivalence point which should coincide a rapid change
in the pH values in an acidbase pH curve if that indicator is suitable for determining the end point of the
titration. For example, in a titration between a strong acid and a weak base, the rapid change in pH
occurs over the region below pH 7 so an indicator with a pKInd value above 7, such as phenolphthalein,
pKInd = 9.4, will not be suitable for the titration, whereas methyl red, pKInd = 5.1, will be.
Alternatively, this can be shown diagrammatically on a pH curve.
g) Strong acid with a weak base/b) (as well as a) where any acidbase indicator is suitable)
8 a) In the ammonia/ammonium chloride buffer we have the equilibrium:
NH3(aq) + H+(aq) NH4+(aq)
As ammonia is a weak base we have a high proportion of unprotonated ammonia molecules which will
be available to accept H+(aq) ions from the addition of acid to the buffer solution, minimising the lowering
of the pH.
The buffer also contains NH4+(aq), mainly from the ammonium chloride salt, which are ready to replace
any H+(aq) ions removed from the solution by the addition of a base (as the OH(aq) ions from the base
react with H+ ions in the equilibrium mixture above to form water). The donation of H+(aq) ions from
the ammonium ions minimises the rise in pH on addition of the base.
b) See answers on page 452 in Advanced Chemistry for You (2nd edition).
2+
glass tube
salt bridge
platinum
electrode
0.46 V
Zn
ZnSO4(aq)
Pb
Pb(NO3)2(aq)