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States of matter

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INTRODUCTION :

In previous units we have learnt about the properties
related to single particle of matter, such as atomic size,
ionization enthalpy, electronic charge density, molecular
shape and polarity, etc. Most of the observable
characteristics of chemical systems with which we are
familiar represent bulk properties of matter, i.e., the
properties associated with a collection of a large number of atoms, ions or molecules. For example, an individual molecule of a liquid does not boil but the bulk boils. Collection of water molecules have wetting properties; individual molecules do not wet. Water can exist as ice, which is a solid; it can exist as liquid; or it can exist in the gaseous state as water vapour or steam. Physical properties of ice, water and steam are very different. In all the three states of water chemical composition of water remains the same i.e., H2O. Characteristics of the three states of water depend on the energies of molecules and on the manner in which water molecules aggregate. Same is true for other substances also.

Chemical properties of a substance do not change with
the change of its physical state; but rate of chemical
reactions do depend upon the physical state. Many times in calculations while dealing with data of experiments we require knowledge of the state of matter. Therefore, it becomes necessary for a chemist to know the physical laws which govern the behaviour of matter in different states. In this unit, we will learn
more about these three physical states of matter particularly liquid and gaseous states. To begin with, it is necessary to understand the nature of intermolecular forces, molecular interactions and effect of thermal energy on the motion of particles because a balance
between these determines the state of a substance.

INTERMOLECULAR FORCES :

Intermolecular forces are the forces of attraction and repulsion between interacting particles (atoms and molecules). This term does not include the electrostatic forces that exist between the two oppositely charged ions and the forces that hold atoms of a molecule
together i.e., covalent bonds.

Attractive intermolecular forces are known as van der Waals forces, in honour of Dutch scientist Johannes van der Waals (1837-1923), who explained the deviation of real gases from the ideal behaviour through these
forces. We will learn about this later in this unit. van der Waals forces vary considerably in magnitude and include dispersion forces or London forces, dipole-dipole forces, and dipole-induced dipole forces. A particularly strong type of dipole-dipole interaction is
hydrogen bonding. Only a few elements can participate in hydrogen bond formation, therefore it is treated as a separate category. We have already learnt about this
interaction in Unit 4.

At this point, it is important to note that attractive forces between an ion and a dipole are known as ion-dipole forces and these are not van der Waals forces. We will now learn about different types of van der Waals forces.

Dispersion Forces or London Forces :

Atoms and nonpolar molecules are electrically symmetrical and have no dipole moment because their electronic charge cloud is symmetrically distributed. But a dipole may develop momentarily even in such atoms and molecules. This can be understood as follows. Suppose we have two atoms ‘A’ and ‘B’ in the close vicinity of each other. It may so happen that momentarily electronic charge distribution in one of the atoms, say ‘A’, becomes unsymmetrical i.e., the charge cloud is more on one side than the other. This results in the development of instantaneous dipole on the atom ‘A’ for a very short time. This instantaneous or transient
dipole distorts the electron density of the other atom ‘B’, which is close to it and as a consequence a dipole is induced in the atom ‘B’.

The temporary dipoles of atom ‘A’ and ‘B’ attract each other. Similarly temporary dipoles are induced in molecules also. This force of attraction was first proposed by the German physicist Fritz London, and for this reason force of attraction between two temporary dipoles is known as London force. Another
name for this force is dispersion force. These forces are always attractive and interaction energy is inversely proportional to the sixth power of the distance between two interacting particles (i.e., 1/r 6 where r is the distance between two particles). These forces are
important only at short distances (~500 pm) and their magnitude depends on the polarisability of the particle.