Imperfections or Defects in a Solid
Last Updated : 11 Feb, 2022
Matter can exist in broadly three states named solids, liquids, and gases. Solids are those substances that have short intermolecular forces between them that keep molecules (atoms or ions) closely packed. They have definite mass, volume, and shape. Their intermolecular forces are strong and intermolecular distances are short. They are rigid and incompressible.
Solids can be classified as crystalline or amorphous based on the nature of order present in the arrangement of their respective constituent particles. A crystalline solid is a large number of small crystals. These crystals have a definite characteristic geometrical shape. The arrangement of particles inside these crystals is ordered and is repeated on all three dimensions.
Imperfections or Defects in Solids
Though crystalline solids are arranged in short-range and long-range order, the crystals are not perfect. A solid usually consists of a large collection of small crystals. These small crystals have defects or imperfections in them.
Defects occur in crystals when the crystallization process takes place at a very fast or moderate rate. Single crystals are formed when the crystallization process takes place at an extremely slow rate. We consider the defects to be irregularities in the arrangement of constituent particles. Defects are considered to be of two types: Point defects and Line defects.
Point defects are the deviations or irregularities from the model arrangement around a point or an atom in a crystalline substance, whereas line defects are the irregularities or deviations from the model structuring arrangement in complete rows of different lattice points.
These irregularities are called crystal defects. Point Defects are of three types:
- Stoichiometric Defects
- Impurity Defects
- Non-Stoichiometric Defects
Stoichiometric Defects
Stoichiometric Defects are basically the point defects that don't disturb the stoichiometry of the given solid. Stoichiometry is the relationship between the given quantities of reactants and respective products before, during, and following the chemical reactions. Stoichiometric Defects are also called intrinsic or thermodynamic defects.
In the crystals, when some lattice sites are left vacant, the crystal is said to have a vacancy defect. This causes a decrease in the density of the given substance. This defect can also form when the substance is heated.
Vacancy Defect In the crystals, when some constituent particles occupy an interstitial site, the crystal is said to have an interstitial defect. Contrary to vacancy defect, this causes an increase in the density of the given substance.
Interstitial Defect Note: Vacancy and Interstitial Defects are observed in non-ionic solids. Ionic solids need to maintain electric neutrality. Thus, they do not have simple Vacancy and Interstitial defects but have Frenkel and Schottky Defects.
This defect is present in ionic solids. The smaller ion (mostly the cation) gets dislocated from its normal site and gets moved to an interstitial site. This shift in ion creates a vacancy defect at the original site and an interstitial defect at the new location. Due to this, the Frenkel defect is also called the dislocation defect. It doesn't affect the density of the solid as the ion is still present in the structure. This defect is found mostly in ionic substances where there is a large difference between the size of the ions. For example, ZnS, AgCl, AgBr, and AgI show Frenkel defects as Zn2+ and Ag+ ions are small in size.
Characteristic of Frenkel Defect
- This defect occurs exclusively when the cations are smaller than the anions. There are no changes in chemical attributes as well.
- The Frenkel defect also has no effect on the density of the solid, hence both the volume and mass of the solid are conserved.
- Substances retain their electrical neutrality in such instances.
- As the like charge ions get closer together, the dielectric constant rises.
- Because of the presence of unoccupied lattice sites, materials with Frenkel defects exhibit conductivity and diffusion in the solid state.
- The Frenkel flaw reduces the lattice energy and stability of crystalline solids. This flaw has an impact on the chemical characteristics of ionic compounds.
- The solid's entropy rises.
Frenkel Defect The Schottky defect is like a vacancy defect in the ionic solids. The number of mission cations and anions are always constant in this defect to uphold electric neutrality. Just like a simple vacancy defect, the Schottky defect also ends up decreasing the density of the given substance. The number of defects in ionic solids is pretty significant. This defect can be observed in ionic solids having cations and anions of similar sizes. For example, KCL, NaCl, CsCl, and AgBr.
Characteristics of Schottky Defect
- The size difference between cation and anion is negligible.
- Both cation and anion depart the solid crystal.
- Atoms are also permanently ejected from the crystal.
- In most cases, two positions are created.
- The density of the solid decreases significantly.
Schottky Defect Exception: AgBr shows both Frenkel and Schottky defects.
Impurity Defects
In impurity defects, foreign components or impurities replace the position of existing ions. For example, if molten NaCl is crystallized in the presence of SrCl2, some of the sites of Na+ ions can be occupied by Sr2+ ions. To maintain electric neutrality, each Sr2+ ion will replace two Na+ ions. Sr2+ ion occupies the site of one Na+ ion and the other Na+ ion site remains vacant. Thus, the number of vacancies created is also equal to the number of Sr2+ ions present.
Other examples of impurity defects are CdCl2 and AgCl.
Impurity DefectNon-Stoichiometric Defects
A large number of nonstoichiometric inorganic solids are known which contain the constituent elements in a non-stoichiometric ratio due to defects in their crystal structures. These defects are of two types:
- Metal excess defect
- Metal deficiency defect
Metal excess defect due to anionic vacancies - this defect is observed in alkali halides like NaCl and KCl. In this defect, crystals have an excess of cation because the anion present combines with an external ion to form another compound. For example, when NaCl crystals are heated in presence of sodium vapors, the Cl- ions diffuse and form NaCl with the sodium vapor. Thus, the crystals now have an extra Na+ ion present. This anionic site is occupied by an unpaired electron. We call this site an F-center. This word is derived from the German word Farbenzenter for color center). This gives off a yellow color to the NaCl crystals. The color appears from the excitation of these electrons when they absorb energy from the visible light falling on the crystals. Just like the above cases, excess Lithium makes LiCl crystals pink and excess Potassium makes KCl crystals violet (or lilac).
Consequences of metal excess defect
The existence of free electrons in crystals with metal excess flaws causes them to be coloured. Because of the presence of free electrons, crystals with metal excess flaws conduct electricity and are semiconductors. Because the electric transport is mostly accomplished by "excess" electrons, these are referred to as n-type (n for negative) semiconductors. Because of the existence of unpaired electrons at lattice sites, crystals with metal excess defects are often paramagnetic. When the crystal is exposed to white light, the trapped electron absorbs some of it in order to be stimulated from the ground state to the excited state. Color is created as a result of this. These are known as F-centres. Positive ion vacancies accompany such surplus ions. These vacancies serve the same purpose as anion vacancies in trapping electrons. V-centres are the colour centres that result from this process.
F-center in a crystal The metal excess defect is caused by the presence of extra cations at the interstitial sites - at room temperature, Zinc oxide is white. When it gets heated, it loses oxygen and turns from white to yellow.
ZnO ⇢ Zn2+ + ½O2 + 2e- (in presence of heat)
As you can see in the above equation, there is now an excess of Zinc in the crystal and its formula becomes Zn1+xO. The extra Zn2+ ions get shifted to interstitial sites and the respective electrons to neighboring interstitial sites.
As we know, it is tough to prepare several solids in stoichiometric composition. These solids have less amount of metal as compared to stoichiometric proportion.
A perfect example of this type is FeO which is mostly found with a composition of Fe0.95O. It may range from Fe0.93O to Fe0.96O. In the crystals of FeO, there is a loss of positive charge due to the missing Fe2+ cations. The loss of charge is covered by the presence of the Fe3+ ions to make the substance electrically stable.
Sample Problems
Question 1: Which defects decrease the density of the substance? Explain those defects.
Answer:
Density of substance decreases in Vacancy defect and Schottky Defect.
In the crystals, when some lattice sites are left vacant, the crystal is said to have a vacancy defect. This causes a decrease in the density of the given substance. This defect can also form when the substance is heated.
Schottky defect is basically a vacancy defect in given ionic solids. The number of mission cations and anions are always constant in this defect to uphold electric neutrality. Just like a simple vacancy defect, the Schottky defect also ends up decreasing the density of the given substance. The number of defects in ionic solids is pretty significant. This defect can be observed in ionic solids having cations and anions of similar sizes. For example, KCL, NaCl, CsCl and AgBr.
Question 2: What is the dislocation defect? Give examples.
Answer:
Frenkel defect is present in ionic solids. The smaller ion (mostly the cation) gets dislocated from its normal site and gets moved to an interstitial site. This shift in ion creates a vacancy defect at the original site and an interstitial defect at the new location. Due to this, the Frenkel defect is also called the dislocation defect. It doesn't affect the density of the solid as the ion is still present in the structure. This defect is found mostly in ionic substances where there is a large difference between the size of the ions. For example, ZnS, AgCl, AgBr, and AgI show Frenkel defects as Zn2+ and Ag+ ions are small in size.
Question 3: Which compound has both Frenkel and Schottky defects?
Answer:
Silver Bromide (AgBr) is the compound that shows both Frenkel and Schottky defects.
Question 4: Explain how defects are different in non-ionic and ionic solids.
Answer:
Vacancy Defect - In the crystals, when some lattice sites are left vacant, the crystal is said to have a vacancy defect. This causes a decrease in the density of the given substance. This defect can also form when the substance is heated.
Interstitial Defect - In the crystals, when some constituent particles occupy an interstitial site, the crystal is said to have an interstitial defect. Contrary to vacancy defect, this causes an increase in the density of the given substance.
Vacancy and Interstitial Defects are observed in non-ionic solids. Ionic solids need to maintain electric neutrality. Thus, they do not have simple Vacancy and Interstitial defects but have Frenkel and Schottky Defects.
Question 5: Why does NaCl acquire yellow color when subjected to excess sodium?
Answer:
When NaCl crystals are heated in presence of sodium vapours, the Cl- ions diffuse and form NaCl with the sodium vapour. Thus, the crystals now have an extra Na+ ion present. This anionic site is occupied by an unpaired electron. We call this site an F-center. This word is derived from the German word Farbenzenter for colour centre). This gives off a yellow colour to the NaCl crystals. The colour appears from the excitation of these electrons when they absorb energy from the visible light falling on the crystals. Just like the above cases, excess Lithium makes LiCl crystals pink and excess Potassium makes KCl crystals violet (or lilac).
Question 6: What are line defects?
Answer:
Line defects are the irregularities or deviations from the model structuring arrangement in complete rows of different lattice points.
Question 7: What are thermodynamic defects? Mention its types.
Answer:
Stoichiometric Defects are basically the point defects that don't disturb the stoichiometry of the given solid. Stoichiometry is the relationship between the given quantities of reactants and respective products before, during and following the chemical reactions. Stoichiometric Defects are also called intrinsic or thermodynamic defects.
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