LIQUIDS ‘The liquid state may be regarded as the intermediate state between the gaseous and the solid states of matter. Liquids and gases are both fluids and flow readily under applied | stress, but like solids, liquids are dense, relatively incompressible and have properties that are largely determined by the nature and strength of intermolecular forces. 21 STRUCTURAL DIFFERENCE BETWEEN GASES, LIQUIDS AND SOLIDS In gases, the molecules are widely separated from one another, moving freely in space and are in a completely random arrangement. But in liquids, the molecules are close to each other and there is very little space between the molecules. However, the random movement of the molecules may often leave holes at places in the bulk of the liquid. In solids, the molecules are closely packed in the form of a crystal lattice, are not free to move, and possess vibratory motion only. ‘The major différence in the microscopic structure of gases liquids and solids involves randomness and order. A gas has essentially no order. A liquid has short-range order and long-range disorder. The molecules in a small region of the liquid may have an orderly arrangement, but this arrangement is not repeated throughout the liquid. Solids have both long-range as well as short-range order. A solid has its constituent particles arranged in a regularly ordered internal array. Short-range order Long-range order Solid Liquid 2.1, Order and Disorder in Gases, Liquids and Solids. lecule is not surrounded by a definite number of lecule is surrounded by a definite number of gion. Ina solid, the number of atoms or Fig. In a gas any particular mol: molecules, while in a liquid any particular mol molecules, arranged in a regular manner in a small re molecules at any distance from the individual atom is fixed, ‘Scanned with CamScanner———— a ATEXT BOOK OF PHYSICAL Heyy 40 id has a defini A gas has no definite surface while a liquid as well as solid has a definite g the surface. the molecules cannot easily eee liquids show the presence of short-range oy, oy The X-ray-diffraction stu ecules. The structure of a liguig 9% range disorder and holes in the packing of molecu . the molecules. lepey somewhat on the geometry and intermolecular forces o! Tey ea | | 2.2 — Interactions Among the Molecules in Liquids. Intermolecular forces in liquids are collectively called van der peas forces, forces are essentially electrical in nature and result from the attraction of char; sigh. The principal kinds of intermolecular attractions are 1. Dipole - Dipole attraction 2. London Forces —_3- Hydrogen bonding. The relative size of these interactions are important in order to relative effects. 88 of opp understand iy The normal covalent bonds are almost 40 times the strength Covalent bonds are almost 200 tithes the strength of dipole - dipole foreés, times the size of London dispersion forces. * 1- Dipole - Dipole Attractions of hydrogen toni, » and more than 4 Dipole-dipole attractions exist between polar molecules. This requires the presence of polar bonds. and an unsymmetrical molecule. These molecules have a permanent separation of positive and negative charge. For example, in HCI molecule the H end of HCl has permanently slightly positive charge and Cl end of HCl has a permanent slight negative charge. The H atom in one molecule is attracted to the Cl in a neighobour. O. a So, whenever the molecules are close a “UO --O-O~ to each, they tend to line up. The Fig.2.2 Weak attractions between polar Positive end of one molecule attracts . HCI molecules ji the negative end of the other molecule ‘and these electrostatic forces of attraction are called ai The intermolecular force is w attraction is one of the stronger inter: 2. London Dispersion Forces lipole-dipole forces, eak compared to covalent bond, but this dipol-dinlé molecular attractions, = ‘Scanned with CamScannercnep2 soose __uiauips A Electrostatic attraction TE) 5-0-3 Helium atom | Helium atom 2 ig.2.3 Explanation of London Forces ‘The nucleus of one atom attracts electrons from the neighbouring atom. At the same time, the electrons in one particle repel the electrons in the neighbour and create a short | lined charge imbalance. These temporary charges in one molecule or atom attract opposite charges in nearby molecules or atoms. A local slight positive charge 6* in one molecule will be attracted to a temporary slight negative charge 5 in @ neighbouring molecule. The momentary force of attraction created between instantaneous dipole and the induced dipole is called dipole-induced dipole interaction or London force. g- Hydrogen Bonding covalently bonded toa small, highly electronegative atom and a lone pair of electrons on highly electronegative in another mnaleeule is called hydrogen bonding". Hydrogen bond is represented By & dotted or dashed «than a eovalént or ionie bond but itis much stronger than the van der "The electrostatic attraction between a hydrogen atom line. It is much weake Waals attraction forces. It should be noted that: mm can participate in hydrogen bonding if it is bonded to 0, NorF () A hydrogen ator omic size. which have highly electronegativity and small at ker than a normal covalent bond. The (i) Hydrogen bond is longer and much weal ire in the range 8-42 kJ/mole. energies (strengths) of the hydrogen bonds (i) Hydrogen bonding results in long chains or clusters of a large number of associated molecules like many tiny magnets. {v) Like a covalent bond, hydrogen bond has a preferred bonding direction. This is attributed to the fact that hydrogen bonding occurs through p orbital which contain the lone pair of electrons on O, N or F atoms. When hydrogen atom is covalently bonded to highly electronegativity atom such as N. 0 or F, it carries partial positive charge and jnteracts with the lone pair of highly of another molecule nearby. In general, whenever polar molecules come (6°) of one molecule interacts with the negative end (6-) tion between them and thus these molecules will .s, In water and’HF these ‘interaction can electronegative atom near to one another, the positive end of another because of electrostatic attract associate together to form large clusters of molecule be represented as ‘Scanned with CamScanner2 ATEXT BOOK OF PHYSICAL CHEMISTRY | Hydrogen bonding in HO { i | | Hydrogen bonding in HF Types of Hydrogen Bond. There are two types of hydrogen bonds. (i) Intermolecular H-bonding (Association). This type of hydrogen bonding is between two or more similar of different molecules. As a result of this type of bonding two or more molecules are associated together. Ammonia, water, hydrogen fluoride, alcohols, carboxylic acids etc. are the examples containing intermolecular H-bonds. Hydrogen bonds between alcohol molecules Acetic acid dimer (ii) Intramolecular H-bonding (Chelation). In some cases a hydrogen bonding can occur within a single molecule. This type of hydrogen bonding is between two functional groups of the same molecule and thus leads to the formation of a ring structure. This type of hydrogen bonding is therefore, a kind of chelation, o-hydroxybenzaldehyde (i.e; salicylaldehyde), o-nitrophenol, o-chlorophenol are the examples containing intramolecular hydrogen bonding. ~ O~ or Oy Oo H ‘ o-nitrophenol Solicylaldehvde Hydrogen bonding has a significant effect on the physical properties (boiling points, solubility of organic compounds). If hydrogen bonding is possible between solute and solvent, this greatly increases solubility of a eubstance. 2.3 SURFACE TENSION . Molecules in the interior of aliquid are attracted equally in all directions by the ‘Scanned with CamScannerchap. jonap.21 Liquios 43 molecules around it, and are thus subjected to a halanced set of forces, wherea’ molecules at the surface are attracted only towards the interior as shown in Fig.2.4. The attractions pull the surface jayer toward the centre, because of the difference in the strength of interactions of the surface molecule with the molecule in the vapour phase and one that is Jp the bulk below it, As a result of the inward nttraction the surface of the liquid experiences an attractive force known as surface tension and surface pig.2.4 ; sehaves like a stretched membrane. That is why be sat es an the surface of any liquid tends to minimize its below the surface of A ina a spherical shape because a sphere has the minimum surface surface area. A droplet assizmes area for a given volume. defined as the force in newtons acting at right angle on a unit 2 of a liquid. It is denoted by 7 (gamma). The SI unit of surface 1), Note that the units of Nm-!, are equivalent to joules per The Surface Tension is length (1m) along the surface tension is newton per meter (Nav square meter, Jm™. Surface tension is related to the attractive forces between molecules. Liquids with relatively large surface tensions. The large surface tension of tensive hydrogen bonding in the water structure sion of a liquid decreases with increasing Jarge attractive forces have water is mainly due io more ex Bffect of Temperature. The surface ten becomes zero near the critical temperature. ‘a change in surface tension of a liquid. When there is an increase in kinetic energy of liquid molecules (KE « 7), “cular forces. It results in decrease in the inward pull the liquid. In other words, surface tension decreases with nd J. Shields gave the following relationship between vemperature and ‘A change in temperature causes temperature increases, thereby decreasing intermole functioning on the surface of increase in temperature. W. Ramsay ai and surface tension of a liquid "8 (4) = ker-9 TO where y= surface tension of a liquid at a temperature 7, M= Molar mass of the liquid; D = density of liquid at temperature "I". Te = Critical temperature of the liquid, k is a constant ture coefficient). According to this equation, the surface tension becomes zero, when temperature (temperat T=T. Capillary Action. The rise or fall tension of the liquid. Whether a depressed, like. mercury, depends on cohesion between the liquid molecules themselves, liquid and the walls of the tube. These makes with the walls of the tube. If a contact ant is related to the surface of a liquid. in a capillary tube is lary, like water, or is liquid rises in a glass capil the relative magnitude of the forces of and the forces of adhesion between the forces determine the contact angle 8, which.the liquid gle is Jess than 90, the liquid is said to wet ‘Scanned with CamScanner44 A TEXT BOOK OF PHYSICAL CHEMISTRY the surface and a concave meniscus is formed. If the contact angle is greater than 90°, the liquid doés not wet the surface and. a convex meniscus is formed. Surface tension acting along circumference The formation of a concave meniscus by a liquid that wets the glass leads to a capillary rise, whereas the formation of a convex meniscus leads to the depression of the liquid (which does not wet the glass) in a capillary tube. (@) () Fig.2.5:(a): Rise of liquid in a capillary tube; (b) :_ Angle of Contact. 24 MEASUREMENT OF SURFACE TENSION ‘The methods commonly employed for the measurement of surface tension are: 1. The Capillary Rise Method. A fine capillary tube of radius 'r' vertically immersed in a test liquid that wets glass. The liquid rises to a certain height ‘h’ until the force of surface tension pulling the liquid upward is counterbalanced by the downward hydrostatic force. is The force of surface tension (i.e., upward force) acting along the total circumference of the tube is 2nr ycos 0. The hydrostatic force (c., downward force) is equal to the product of pressure and area of cross-section of the tube (© ghdar’). But Upward force. = Downward force 2arycos@= ghd xr? Fig.2.6:The Capillary Rise Method] _ ghdr Y= 2088 ~ @ where yis the surface tension, d is the density of the liquid, g is the acceleration due td gravity, and @ is the contact angle. For most liquids, 0 is essentially zero, and cos 0 = Therefore, Eq.(1) reduces to _ ghdr 4 m3 a | Im order to caleulate the value of y, one needs to know the values of g,h,d and r. ‘Scanned with CamScannerAlternatively, jonap.2) Lu y, The Torsion Balance (Du Nouy's Torsion Balance) Method. This method is often employed for the quick determination ofsurface tension of a liquid. In this method, the force required to detach a platinum ring (Du Nouy ring) from the liquid surface is measured. This force ( F) is exactly equal to the downward pull due to surface tension acting along the circumference of the ring. wice the length of the circumference @x2 xR) is taken, since the liquid is in ith both the inside and outside of contact Wi ring, Fig.(@2.7). Thus = ace F=4nRy or Y> Ga ‘The apparatus employed is shown in Fig.2.8 ‘A thoroughly cleaned Pt-ring of radius dat zero by means of a screw S and torsion wire T is so adjusted that the beam B is in its horizontal position, The height of the dish D containing the test liquid is made to touch the ring by regulating the screw W. The knob K on the circular scale is turned slowly until the ring is detached from the surface of the liquid. ‘The reading shown by the pointer on the scale gives the force F. The surface tension is then calculated from Eq.(3). the force requ ‘The pointer P is fixe measured by the ang! of torsion @, will be proportion: of the liquid acting on it. Thus ya 8 and for water, yw = Ow : 6 By dividing, we get tig Yw We Knowing the value of yw , we can calcul Drop Formation Method. Th capillary tube dep ‘The drop is supported 3 falling from the end of @ size of the capillary end. at the outer circumferen balanced, the drop breaks. Thus at the point of ired to detach the ring frot Je through which the pointer P moves on ‘al to the downward pulfon the ring late the surface tension, y, for @ e size and hence the weight ends upon the surface tensio} ce of the tube. The weight of drop. |QUIDS 45. Fig.2.7:Two films pulling the ring, @) 'R’ is suspended by a hook on the beam B. Fig.2.8. Du Nouy’s torsion balance. m.the surface of the liquid is the graduated scale. The angle due to the surface tension (Experimental liquid) (Standard reference liquid) 8 y= 9, . 4) or ny liquid. 1 of a drop of a liquid mn of the liquid and the ard force of surface tension acting by the upw: pulls it. When the two forces are breaking ‘Scanned with CamScanner> A TEXT BOOK OF PHYSICAL CHEMISTRY 46 y.2nr = W= mg = Vdg ~~ (6) where, r is the radius of the capillary tube, Vis the volume of the drop and d 3 is density This equation being a basis of the drop method is used for the comparison o surfae tensions of different liquids. | @) Drop Weight Method. In this method, the mass of a single drop of liquid, and that of reference liquid (say water) is determined. Then from Eq.(6), W,= mg = 2nry, and W, = mog = 2nr ty oe = ©) Therefore % 7 my Knowing the surface tension of reference liquid, that of the experimental liquid can be determined. (ii) Drop- Number Method. Instead of finding the weights of single drops, it is easier to count the number of drops formed from an equal volume of two liquids. If n, and n, are the number of drops produced from the same volume V of the two liquids, then v The volume of a single drop of liquid 1 = i v The mass of a single drop of liquid 1 =a 4 , -v Similarly, the mass of a single drop of liquid 2 =a Then from Eq(6), th _ Wind, _ rgd, hh ~ Win)d, ~ nd, oon o ‘Thus 7, can be determined easily provided the other quantities are known. The densities of the two liquids can be determined with the help of a pyknometer or specific gravity bottle. ‘The instrument used for determining surface tension is called stalagmometer , which consists of a bulb fuséd with a capillary tube as shown in Fig.2.9. The stalagmometer is thoroughly cleaned and water is sucked up to the upper mark A. The water is allowed to flow and the number of drops is counted until the lower mark B is reached. Next the Surface tension experiment is repeated with the other (experimental) acts along liquid and surface tension of the liquid can be . circumference determined by using the Eq.(7). For reference liquid water, Eq.(7) can be written as: weight of drop Fig.2.9. Stalagmometer. ath tw Ne dy ny tw ‘Scanned with CamScanner