GROUPS 13 & 14

The Boron & Carbon Groups

Student Learning Outcomes
● describe oxidation states and trends in physical properties in group 13 elements
(i.e. ionisation energy, electronegativity, atomic radius, melting and boiling point);
● describe the chemical reaction of group 13 elements with water, oxygen and
chlorine;
● Identify instances of the anomalous behaviour of Boron and explain the reason for
such observations
● List uses of the group 13 elements
● Identify and describe the diagonal relationship between Beryllium and Aluminium
● Describe the extraction and isolation aluminium
The Boron Group
● Valence electron configuration - ns1np1
● Common oxidation states - 0,+3, +1
● Metallic character increases down the
group
● Low melting and boiling points
EXCEPT Boron
● Density increases down the group
● Silver, good conductor of heat and
electricity
PHYSICAL PROPERTIES

● Boron is a hard, black coloured high melting (due to very strong crystalline
structure) non metallic solid

The IE of Boron are much larger than those of the other elements because the
valence shell of Boron is relatively small and compact with very little nuclear shielding
● The IE of the other elements are comparable even though successive energy
levels are further away from the nucleus because IE expected from larger
atomic radii is balanced by an increase in effective nuclear charge
● The elements EXCEPT Boron form the +3 ion in the formation of ionic
compounds
● The stability of +1 oxidation state increases down the group - inert pair effect
CHEMICAL PROPERTIES

● Characterised by the electron deficient nature of the elements, the group 13

elements are Lewis Acids
● Solid aluminium chloride is an ionic solid , however gaseous aluminium
chloride is a electron deficient compound which forms dimers Al2Cl6 to satisfy
its valency
● Boron satisfies its octet in its hydrides by either forming hydrogen bridges

● OR by forming adduct compounds with electron rich compounds such as NH3

BF3 + :NH3 → F3B:NH3

● Basicity of oxides increases with increasing metallic character; B2O3 dissolves

to give a weakly acidic solution, Al2O3 is amphoteric and the other oxides are
basic
USES OF THE GROUP 13 ELEMENTS

● Alum, Al2(SO4)3 used in the treatment of municipal water

● Forms strong, lightweight alloys with copper and magnesium for aircraft
bodies and parts
● High resistance to corrosion - extensively used to make beverage containers
(soda drinks cans)
● Weak solutions of boric acid are used in eyewash
● Boron oxide is used in the production of borosilicate glass.
● Aluminum oxide is the main ore of aluminum and is used as an abrasive in
sand paper, in sanding and cutting tools and toothpaste
Isolation of Aluminium - Bayer Process
● 25% of the ore bauxite contains impurities such as iron(III)oxide, Fe2O3 and
silicon dioxide, SiO2.
● Before being electrolysed all these impurities must be removed
1. The ore is treated with 30% NaOH which reacts with the amphoteric
aluminium oxide and acidic silicon dioxide. Fe2O3 is basic and does not
dissolve
SiO2(s) + 2 NaOH(aq) + 2H2O(l) → Na2Si(OH)6(aq)

Al2O3(s) + 2 NaOH(aq) + 3H2O(l) → 2 NaAl(OH)4(aq)

The solid impurities are filtered from the mixture

2. Carbon dioxide is then bubbled through the filtrate. In solution carbon dioxide
forms a weak acid, carbonic acid – H2CO3 which reacts with the aluminate ions in
solution to precipitate aluminum hydroxide, Al(OH)3.

CO2(g) + H2O(l) ⇋ H+(aq) + HCO3-(aq)

Al(OH)4-(aq) + H+(aq) → Al(OH)3(s) + H2O(l)

The Aluminum hydroxide is removed and dried at high temperatures, which

converts it to the oxide.
Al(OH)3(s) → Al2O3(s) + 3H2O(g)
The Hall Process
● The melting point of Aluminum oxide is very high, 2030⁰C, so it is dissolved in
molten cryolite, Na3AlF6 to give a mixture that is electrolysed at ~1000⁰C
Be & Al
● Beryllium, in group II and Aluminum, in group III are the next pair of diagonally
related elements
● Both form oxoanions in strong base: berylate, Be(OH)42- and aluminate,
Al(OH)4-
● Both have bridge bonds in their chlorides and hydrides
● Both form oxide coatings impervious to reaction with water, and both oxides
are amphoteric, extremely hard and high melting
● Although their atomic and ionic radii differ, the small highly charged Be2+ and
Al3+ ions polarize nearby electron clouds strongly. Therefore, some Aluminum
compounds and all Beryllium compounds have significant covalent character
GROUP 14
Student Learning Outcomes
● describe oxidation states and trends in physical properties in group 14
elements (i.e. ionisation energy, electronegativity, atomic radius, melting and
boiling point);
● describe the chemical reaction of group 14 elements with water, oxygen and
chlorine;
● List uses of the group 14 elements
● Identify and describe the diagonal relationship between Boron and Silicon
● Define and explain the occurrence of the ‘inert pair effect’ with relevant
examples
● Define and identify the occurrence of allotropy
Group 14 - Carbon Group
● Valence electron configuration - ns1np2
● Common oxidation states - 0,+4, +2, -4
● Metallic character increases down the
group
● Electronegativities are generally low
● Decreasing hardness and melting point
● Density increases down the group
INERT PAIR EFFECT

● The tendency of electrons in the outer s-orbital to remain unionised

● This is due to the poor shielding ability of ‘d’ and ‘f’ orbitals (because of their
shape)
● Therefore, in atoms with such electrons, the outer s electrons are pulled more
strongly towards the nucleus and are less available to take part in bonding
● This effect is observed in the larger elements of groups 13 to 15
● In Group 14 the +2 oxidation state becomes more stable as the group is
descended
CHEMICAL PROPERTIES
Reaction with halogens
● The elements are oxidized by the halogens
● The tetrahalides formed are easily hydrolysed, with the exception of carbon
tetrachloride, CCl4 which has no available orbital to accept a lone pair from
water.
Si(s) + 2 Cl2(g) → SiCl4(l)

SiCl4(l) + 2 H2O(l) → SiO2(aq) + 4 HCl(g)

● The dichloride becomes more stable as the group is descended.

Lead(IV)chloride, PbCl4 decomposes to form lead(II)chloride, PbCl2 and
chlorine gas, Cl2
Reaction with oxygen

● The group IV elements react with oxygen readily

● Carbon forms simple molecular dioxide, CO2 and monoxide, CO
● Silicon dioxide, SiO2 has a giant structure similar to that of diamond. The
resulting structure, quartz, is hard and has a high melting temperature
● Germanium dioxide, GeO2; tin(IV)oxide, SnO2 and lead(IV)oxide, PbO2 all have
giant structures
● On descending the group there is the expected trend from acid to base – carbon
and silicon dioxide being acidic, germanium and tin dioxide being amphoteric
and lead(II)oxide being basic.
Reaction with hydrogen
● Carbon forms a large number of hydrides with rings and chains of unlimited
lengths and varying degrees of branching. This group of compounds are called
hydrocarbons
● They result from carbon’s ability to catenate – form stable chains and rings;
and its ability to form multiple bonds.
● The ability to catenate decreases down the group as the elements get larger
and the element to element bonds, E ------ E, become longer and weaker
● Silica forms silanes, germanium forms germanes with chain lengths up to six
● Tin and lead form a single hydride each, stannane, SnH4 and plumbane, PbH4
respectively.
● Carbides are binary compounds formed between carbon and other elements
● Like hydrides they can be classified as saline, covalent and interstitial
● Carbon is the only Group 14 element which forms an anion
● In the saline carbides these are C22- and C4-.
● Carbides are hard substances with high melting points.
ALLOTROPES - different forms of the same element
Allotropes of C - Graphite and Diamond
IMPORTANT COMPOUNDS
● CO2 is essential to life – used by plants in photosynthesis
● NaHCO3 – used as baking soda for cooking and as in fire-extinguishers
● CH4 – major component of natural gas; used as fuel and for the production of
hydrogen gas
● SiO2 - used in the manufacture of glass and ceramics
● Silicon carbide (SiC) has diamond-like structure; used to make abrasive and
heat resistant ceramics
● SnF2 – additive in toothpaste to prevent cavity;
● PbO – used in ceramic glaze, and cement;
● PbO2 – oxidizing agent and battery electrodes;
● PbCrO4 – for making yellow pigment for paint
Boron & Silicon

● Boron and silicon are the elements in the third diagonal relationship
● Both exhibit the electrical properties of a semiconductor
● Both elements and their mineral oxoanions, borates and silicates, occur in
extended covalent networks
● Both boric acid, B(OH)3 and salicylic acid, Si(OH)4 are weakly acidic
● Both elements are flammable, low melting compounds with hydrogen,
boranes and silanes – that act as reducing agents