Pause for a moment and just try to imagine a world where carbon was not there, an element that acts as the backbone for all kinds of organic life. From the carbon dioxide we exhale to the diamond engagement rings that speak of love, carbon surrounds us through the environment. However, carbon is just one member among the interesting elements of group 14 of the periodic table; otherwise, it is known as the carbon family. This group consists of carbon, C, silicon, Si, germanium, Ge, tin, Sn and lead, Pb. Each of these elements, in fact, has a very big impact on the different industries and applications we can have in our daily lives. For example, silicon forms the backbone of the electronics industry, including the one that gets the job done for us with our computers, smartphones, and other devices.
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Electronic Configuration
The valence shell electronic configuration of these elements is ns2np2. The inner core of the electronic configuration of elements in this group also differs.
Covalent Radius
There is a considerable increase in covalent radius from C to Si, thereafter from Si to Pb a small increase in radius is observed. This is due to the presence of completely filled d and f orbitals in heavier members.
Ionization Enthalpy
The first ionization enthalpy of group 14 members is higher than the corresponding members of group 13. The influence of inner core electrons is also visible here. In general, the ionization enthalpy decreases down the group. The small decrease in $\Delta_{\mathrm{i}} \mathrm{H}$ from Si to Ge to Sn and a slight increase in $\Delta_{\mathrm{i}} \mathrm{H}$ from Sn to Pb is the consequence of poor shielding effect of intervening d and f orbitals and increase in size of the atom.
Electronegativity
Due to the small size, the elements of this group are slightly more electronegative than group 13 elements. The electronegativity values for elements from Si to Pb are almost the same.
The elements of Group 14 range from non-metal to post-transition metal; this means they do show a qualitative variation in the physical properties down the group. It is because of the addition of electron shells that the atomic radius increases from carbon to lead. A small atomic radius for carbon can give strong covalent bonds, resulting in the hardest natural substance, the diamond, and also one that is soft, graphite. Silicon and germanium are metalloids. They have some of the typical properties of metals and some of the typical properties of nonmetals—moderate electrical conductivities, and they are quite thermally stable. Tin and lead are metals that show common trends, they are malleable and ductile. It conforms to the general decrease in melting and boiling points down the group, except carbon, with a much higher value as a consequence of the very strong covalent bonds within the network structures.
Allotropy
The ability of an element to exist in more than one physical form is called allotropy. All the elements of this group except Pb exhibit allotropy. Carbon has three allotropes i.e, diamond, graphite, and fullerene
Valency
All the elements of this group show tetravalency as they have 4 electrons in their valence shell.
Atomic and Ionic radii
As we move down the group, the radius of these elements increases.
Multiple Bonding
Carbon forms p-p bonding with itself and with S, N, and O. While the other elements of this group form p-d bonding as they have a vacant d-orbital while carbon does not have.
One of the interesting physical properties related to carbon is allotropy. It has a number of allotropes resulting, which include diamond, graphite, graphene, or fullerenes. All these allotropes commonly depict customary physical characteristics of carbon: diamond, for one, being very hard, depicts a good conduction of heat; graphite has lubricating and electrical-conducting properties. In fact, silicon comes in many crystalline forms, the best known being the diamond cubic structure. The bandgap of silicon makes this an extremely important factor for semiconductor devices. Germanium is also somewhat like silicon, although less abundant and not quite so versatile in its uses either. It finds applications in specialized electronic devices. The metal tin exists in two allotropes: white tin, a metallic, ductile conductor of electricity, and gray tin, a brittle, non-metallic semiconductor. Finally, lead is the densest and most metallic member of this family. It is a very malleable metal with good resistance to corrosion and, therefore, finds applications in many kinds of industries.
Hydrides
The carbon family elements play a very meaningful role in many spheres. As far as organic chemistry is concerned, carbon goes without saying that it makes the basic constituent of organic compounds and, therefore, the very backbone of life in the form of organic chemistry. Industrially, the allotropes of carbon have a magnitude of applications, from the creation of tools to lubricants and electrodes, especially because of the semiconductor property that is characteristic of silicon and which, because of its allotropic nature, makes this material the backbone of the electronics industry and of the basic components for the production of integrated circuits and solar cells.
These elements can form halides of the formula MX2 and MX4 (where X = F, Cl, Br, I). Except carbon, all other members react directly with halogen under a suitable condition to make halides. Most of the MX4 are covalent in nature. The central metal atom in these halides undergoes sp3 hybridization and the molecule is tetrahedral in shape. Exceptions are SnF4 and PbF4, which are ionic in nature. PbI4 does not exist because Pb—I bond initially formed during the reaction does not release enough energy to unpair 6s2 electrons and excite one of them to a higher orbital to have four unpaired electrons around lead atom. Heavier members Ge to Pb are able to make halides of formula MX2. The stability of dihalides increases down the group. Considering the thermal and chemical stability, GeX4 is more stable than GeX2, whereas PbX2 is more stable than PbX4. Except for CCl4, other tetrachlorides are easily hydrolyzed by water because the central atom can accommodate the lone pair of electrons from the oxygen atom of a water molecule in d orbital.
All members when heated in oxygen form oxides. There are mainly two types of oxides, i.e., monoxide and dioxide of formula MO and MO2 respectively. SiO only exists at high temperatures. Oxides in higher oxidation states of elements are generally more acidic than those in lower oxidation states. The dioxides — CO2, SiO2, and GeO2 are acidic, whereas SnO2 and PbO2 are amphoteric in nature. Among monoxides, CO is neutral, GeO is distinctly acidic whereas SnO and PbO are amphoteric.
Example 1
Question: Which of the following pairs have equal electronegativity?
1) C and Si
2) Si and Ge
3) Ge and Sn
4) (2) and (3) both
Solution: The electronegativity values for Group 14 elements decrease from carbon to lead, but not in a regular manner due to the filling of d and f orbitals. The electronegativity of carbon (C) is 2.5, while silicon (Si), germanium (Ge), and tin (Sn) each have an electronegativity of 1.8. Therefore, both Si and Ge and Ge and Sn have equal electronegativity values. Hence, the correct answer is option (4).
Example 2
Question: 'X' melts at a low temperature and is a bad conductor of electricity in both liquid and solid states. X is:
1) Carbon tetrachloride
2) Silicon carbide
3) Mercury
4) Zinc sulphide
Solution: Carbon tetrachloride (CCl4) is a non-polar compound with a melting point of −22.92°C. It is a poor conductor of electricity in both liquid and solid states because it is a non-electrolyte and a covalent compound, meaning it consists of molecules with no charge separation. Hence, the correct answer is option (1).
Example 3
Question: The melting point of silicon is:
1) Higher than B
2) Lower than Al
3) Higher than C
4) Lower than C
Solution: The melting points of the elements in Group 14 vary. For example, boron (B) has a melting point of 2553 K, aluminum (Al) has a melting point of 933 K, carbon (C) has a melting point of 4373 K, and silicon (Si) has a melting point of 1693 K. From this data, we see that silicon has a lower melting point than carbon. Hence, the correct answer is option (4).
The elements of Group 14 that fall in the carbon family vary over a diverse set of variations in the physical properties down the group. From the covalent bond of carbon to allotropy, from semiconductor features of silicon and germanium to metallic properties for tin and lead, these elements would all be essential in application. Generally, it is their divergent properties that would hold a central position in aspects of electronics, material science, chemistry, and industry. Knowing the physical properties and the possibilities of usage for an element of group 14, one realizes how important and helpful they are from an academic and also practical point of view.
Carbon has allotropic physical properties. In connection to this matter, a diamond is very hard and provides high thermal conductivity while graphite is very soft, slippery, and electrically conductive. Graphene is basically one atomic layer of carbon atoms known nowadays due to its strength and electrical properties.
• Application: Diamond in instruments that need sharp pointed cutting edges and as a gemstone; graphite as lubricating agents and as electrodes in cells. Graphene is planned for high-performance gadgets and materials because of its properties, which are just mind-blowing.
That is, the electrical conductivity of silicon is good to be modulated, meaning doped, only as required for the application in semiconductors. Its widespread usage can be attributed to the added advantage of availability along with thermal stability, hence its popular use in electronic applications—mainly microchips and solar cells.
Solution: The semiconducting properties of silicon have been put to use in making integrated circuits to power today's myriad of electronic devices. Solar cells based on silicon are a basic building block of renewable energy technology.
There are two essential allotropes of tin: white and gray tin. White tin is a metallic, conductive, and ductile form of the metal, mostly used in alloys and plating. Gray tin is the form in which it has become brittle and nonmetallic; it typically forms at low temperatures and tends to make other tins fall to pieces, a condition known as "tin pest."
Solution: White tin is used for soldering and plating other metals as a means of protecting them against corrosion. Gray tin is rather useless as it turns out to be very brittle and crumbles readily at low temperatures; thus, it needs special care in storage and handling.
It finds application in the unique properties that outweigh its toxicity. Some of the common applications include the use of lead-acid batteries in cars and standby power systems, and in radiation shielding due to its high density, where high effectiveness in blocking X-rays and gamma rays is realized. However, its use is being more and more controlled and restricted in many applications these days.
Solution: All automobile and standby power applications utilize restored lead-acid batteries because they are reliable and relatively cheap. The blocking effect of the radiation of lead is of paramount importance in protecting human health and equipment from damage in a medical or industrial environment.
Although in most ways germanium is semiconducting like silicon, it has a larger refractive index and works better at very low temperatures; it finds special usage in very limited applications involving in the fields of fiber optics, infrared optics, and some kinds of transistors and diodes where its altered characteristics give it an edge, although compared to silicon, germanium is less common and more expensive.
• Solution: Germanium has a brilliant refractive index; thus, it is useful in high-performance fiber optic systems and improves the capabilities of data transmission. The germanium lenses find an application in infrared optics, particularly in thermal imaging cameras. Its semiconductor properties are applied to certain electronic elements where performance at really low temperatures may turn out to be crucial.
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