Surface tension The existence of strong inter-molecular forces of attraction in liquids gives rise to an important property: surface tension.

Consider a molecule somewhere in the body of the liquid. This is attracted equally in all directions by other molecules which surround it, therefore cancel the effect of one another.Consider, next, a molecule near the surface. The downward attractive forces are greater than the upward forces because there are more molecules of the liquid below than in the air above the surface. These unbalanced attractive forces acting downward tend to draw the surface molecules into the body of the liquid and, therefore, tend to reduce the surface to a minimum. Since the attractive forces are more predominant in the bul of the liquid than at the surface, the molecules in the bulk of the liquid are associated with lower energy than at the surface. !n other words, the molecules at the surface possess greater energy than those in the bul . !t is the extra energy of the surface molecules which gives rise to their tendency to move into the bul of the liquid, i.e., the molecules tend to move from a state of higher energy to a state of lower energy. "s a consequence of this transfer, the number of molecules at the surface is less than that in the bul . The distance between any two molecules at the surface, therefore, becomes greater than in the bul .Consequently, the surface molecules tend to move closer to one another in order to acquire a normal distance between them as before. Surface tension, therefore, tends to contract the surface. !t is for this reason that drops of a liquid or bubbles of a gas are spherical in shape. A sphere has a minimum surface for a given volume of a liquid or gas. "s a result of the tendency to contract, surface of a liquid behaves as if it were in a state of tension. Surface tension may be defined as the force in dynes acting at right angles to the surface of a liquid along one centimeter length of the surface. It is generally represented by the symbol and expressed in dynes cm- . Surface tension of water #$.%, &thyl alcohol $$.#, "cetone $'.# at $()C. *+eason- Stronger inter-molecular forces in water than those in organic liquids, Surface energy The effect of surface tension is to reduce the area of the surface to a minimum. !f we wish to increase the area of the surface of a liquid, we have to wor against the force of surface tension. !he work that is required to be done in order to extend the area of the surface of a liquid by sq.cm.is called surface energy of of the liquid . !t is expressed in ergs-cm$. !t may also be put as *dynes . cm, cm -$, i.e., dynes cm-/, which is also the unit of surface tension.Thus0 surface tension is equal to surface energy numerically as well as dimensionally. Some effects of surface tension

/. The effect of surface tension is to reduce the area of the surface to a minimum. 1ence drops of a liquid or bubbles of a gas are spherical in shape as stated before. A sphere has a minimum surface for a given volume. $. The rise of a liquid in a capillary tube*e.g., rise of oil in the wic of a lamp, rise of under-ground water on to the surface of earth, Capillary rise method " method of measuring surface tension Consider a capillary tube lowered in a liquid that wets its surface *e.g., water,.The liquid will rise almost instantaneously up to a certain height depending upon its surface tension and density. The column of the liquid in the capillary is, evidently, being supported by some force acting along the surface of the water. This is force of surface tension. Suppose a liquid of density d, rises in a capillary tube of radius r, through a height h. 2et be the force of surface tension in dynes per cm. Then, the total force due to surface tension, raising the liquid column upward 3 x inside circumference of the capillary, i.e., 3 "# r dynes. 4orce of gravity pulling the liquid downward 3 weight of the liquid column. 5eight of the liquid in the column 3 v dg dynes where v is the volume of the liquid in the tube. 6ut v $ # r"h. 1ence, for equilibrium, "# r $ # r" h dg $ r h dg% " dynes per cm. !t is assumed in the above derivation that the contact angle 7 between the glass and the liquid is 8ero, that is, wetting is perfect. !f this is not so, it can be shown that $ r h dg% "cos 7 This gives us, incidentally, a method of measuring surface tension, nown as the capillary rise method. 4or this purpose, it is required to measure the height *h, through which the liquid rises and the radius*r, of the capillary tube, both in cm.The height is measured by a cathetometer and the radius of the capillary tube by a traveling microscope. The contact angle in most such cases is 8ero. The Drop Weight Method !n physical chemistry, surface tension is usually measured by the drop weight method as this is more convenient. This method is based on the principle that the weight *w, of a drop of liquid, falling from a given capillary tube held vertically is approximately proportional to the surface tension of the liquid. Thus, if surface tensions of any two liquids are / and ", then, / % " 3 w/-w$ 5here w/ and w$ are mean weights of their drops falling from the same capillary tube. The instrument used is nown as stalagmometer. !t is more convenient to count the number of drops formed by a given volume of a liquid than to find the weight of a drop.

Suppose, equal volumes *9, of two liquids, when allowed to fall through the same stalagmometer, form n/ and n$ drops. Then, mean weights of such drops w/ and w$ are given as: w/ 39 d/-n/ w$ 39 d$-n$ 5here d/ and d$ are densities of the two liquids. 1ence / % " 3 w/-w$ 3 9 d/-n/ / 9 d$-n$ 3 n$d/ -n/d$ !f surface tension of one of the liquids is nown, that of the other can be easily calculated. The densities of the liquids may be determined by the usual specific gravity bottle or py nometer method. Procedure The stalagmometer is first thoroughly cleaned with chromic acid mixture and dried. !t is then filled with water up to the mar : by suc ing at the other end of the tube. The water is then allowed to come out in the form of drops which are counted. The number of drops per minute should not exceed $( as otherwise they will not be properly formed. The rate can be controlled with the help of a pinch coc attached to a rubber tube at the upper end of the stalagmometer. The stalagmometer is again thoroughly washed and dried and now filled with the liquid under examination upon the same mar :. The number of drops is counted as before. 2et the number of drops of water and the liquid under examination be n/ and n$ and let d/ and d$ be their respective densities. Then, surface tension of the liquid, n$d/ " -n/d$, where " is the surface tension of water at the same temperature. Interfacial Tension Suppose, two immiscible liquids are present one above the other in a vessel. Then, the force acting per unit length along the interface is called interfacial tension. This is less than the surface tension of the liquid with a higher value. The reason is that the unbalanced forces acting along the surface of each liquid are partly compensated by force of mutual attraction between the molecules of the two liquids. !t may be emphasi8ed that surface tension and interfacial tension involve the same type of force. 5hen one spea s of surface tension of a liquid, it is understood that the force is acting along the surface of separation between the liquid and its vapour.5hen one spea s of interfacial tension, it is understood that the force is acting along the surface of separation of two immiscible liquids in contact with each other. Effect of temperature on surface tension "ccording to the inetic theory, molecular inetic energy is proportional to absolute temperature. The rise in temperature of a liquid, therefore, is accompanied by increase in energy of its molecules. The intermolecular forces of attraction, therefore, decrease with rise in temperature. 1ence surface tension of a liquid decreases with rise in temperature.

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"t critical temperature, since the surface of separation between a liquid and its vapour disappears, the surface tension falls to 8ero. &otvos found that surface tension varies linearly with temperature. 1e suggested that the following expression for the variation of surface tension with temperature: *:-d, $-' 3 a ; k t 5here : is the molecular weight the density and the surface tension of the liquid at the temperature t0 a and k are constants. &%d ' evidently' is molecular volume of the liquid. Assuming this volume to be spherical (since area of a sphere is minimum)' we may take (&%d) "%* as proportional to the molecular surface of the liquid. Since ' the surface tension' is also surface energy per square centimetre' it is evident that the expression (&%d) "%* is proportional to molecular surface energy. "t the critical temperature *i.e., when t 3 t c, the surface tension is 8ero. Substituting these values we may write ( 3 a- k tc a 3 k tc Therefore The &otvos equation, therefore, may be written as: *:-d, $-' 3 k *tc ;t, This equation has been found to be satisfactory in giving variation of surface tension with temperature in the case of a number of liquids over a wide range of temperature. Surface Acti e Agents " number of substances are nown which, when added to water, lower its surface tension. These substances are called surface active agents. Thus liquids li e methanol, ethanol, acetone and acetic acid when added to water lower its surface tension. Salts of higher sulphonic acids and higher amines which behave in this manner. They are all surface active materials. These substances act as detergents. To ta e an example, we may explain the action of soap as a detergent. :ost of the dirt or dust stic s on to grease or oily materials which somehow gather on cloth. "s grease is not readily wetted by water, it is difficult to clean the garment by water alone. The addition of soap lowers the interfacial tension between water and grease so as to facilitate the mixing of the two. The soap molecules get oriented at the interface between water and oil *or grease, in such a way that their polar end *-C<<=a, is dipping in water and the hydrocarbon chain*+-, in the oil. This helps in bringing the two liquid phases in more intimate contact with each other. !n other words' the presence of soap causes emulsification of grease in water. The mechanical action, such as rubbing, etc., releases the dirt.

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!iscosity 9iscosity implies resistance to flow. !t is well- nown that all liquids do not flow equally readily. Those liquids which flow slowly*for example,glycerine,castor-oil,honey and coaltar, are said to have high viscosity while those which flow readily*for example,water,alcohol and ether, are said to have low viscosity. The significance of viscosity may be further elucidated by considering the flow of a liquid through a narrow pipe. "ll parts of the liquid do not move with the same velocity. " thin layer, immediately in contact with the walls of the tube, is almost stationary. &ach succeeding thin layer of the liquid moves with gradually increasing velocity which becomes maximum as the centre of the tube is approached. !he resistance that one part of a liquid flowing with one velocity offers to another part of the liquid flowing with a different velocity is known as viscosity. Alternatively' viscosity may be looked upon as the force of friction between two layers of a liquid moving past one another with different velocities. Suppose a cylindrical liquid layer of area " sq.cm. moves over another similar layer at a distance of S cm.with a velocity difference of u cm.per sec.Then, the tangential force of friction *f,, required to maintain a constant difference of velocity, is given by f 3 ?"u-S

5here ? is a constant at a given temperature, depending upon the nature of the liquid and is nown as the coefficient of viscosity. !f " is / sq.cm., u is / cm.per sec. and S is / cm., then f 3 ?. !he coefficient of viscosity of a liquid may' therefore' be defined as the force in dynes per square centimetre required to maintain a difference of velocity of cm.per sec. between two parallel layers of the liquid held at a distance of cm. from one another. The reciprocal of viscosity is called fluidity and denoted by @. Thus @ 3 /- ?

Determination of !iscosity There are a number of methods of different inds for measuring viscosity. The method commonly employed is based on poiseuilleAs law which connects the rate of flow of a liquid through a capillary tube with the coefficient of viscosity of the liquid and is expressed by the equation: ? 3 # r+ t p % , - l

5here 9 is the volume in c.c.of the liquid flowing in t seconds through a narrow tube of radius r cm. and length l cm.under a hydrostatic *driving, pressure of p dynes per square centimetre and ? is the coefficient of viscosity in poises*i.e., dynes per square centimeter,. Since the hydrostatic pressure p of a liquid column is given by . 3 hdg

5here h is the height of the column and d the density of the liquid, the poiseuilleAs equation may be written as: ? 3 # r+ t h d g % , - l

!t is not necessary to measure all quantities on the right hand side of the above equation. The viscosity of water at different temperatures has been very accurately determined. The usual procedure is to determine the viscosity of a liquid with reference to that of water. This is termed as relati e iscosity. "ll that is done is to measure the times of flow for equal volumes of water and the liquid under examination, through the same capillary. !f t / and t$ are the times of flow of the same volume of water and the liquid, respectively, and ?/ and ?$ are the respective coefficients of viscosity, then ?/- ?$ 3 # r+ t h d g , - l / , - l # r+ t" h d" g The value of h is the same in both cases since equal volumes of both liquids are ta en and, therefore, they stand at the same height. Therefore, ?/- ?$ 3 d t % d" t"

"s#ald$s !iscometer <swaldAs viscometer is used for measuring viscosity by the above method. !t is first thoroughly cleaned with chromic acid mixture and dried. " nown volume of water, usually /( to $B ml.depending upon the capacity of the bulb ", is pipetted into the bulb 6* bulb 6 is bigger than ",.!t is then suc ed into the bulb " with the help of a rubber tube attached at the end C till it rises to the mar :. The time ta en by this water to flow through the capillary tube C& is noted by means of a stop watch. 2et it be t /.The viscometer is dried and the same volume of the liquid under examination is ta en into the bulb 6 *so that the pressure head remains the same, and the process repeated as before. 2et the time of flow now be t $.Then, evidently, ?/- ?$ 33 d t % d" t" 5here d and d" are the densities of the two liquids which can be determined by specific gravity bottle or by py nometer method. Dnowing the coefficient of viscosity of water * ?/,, that of the other liquid * ?$, can easily be calculated. %nit of iscosity "s we have equation, 0 $ f S%Au

Since f is measured in dynes, S in cm. " in cm. $ and u in cm.-sec., 1ence the units of 0 are dynes x cm. / cm.$ x cm.-sec. 3 dynes cm.-$sec.Thus viscosity is measured in dynes sec. -cm $. 4or simplicity, the units of viscosity dynes sec.cm-$ are called poises. Still more convenient units of viscosity are centipoises and millipoises *one millipoise 3 (.((/ poise and one centipoise 3 (.(/ poise,. Elycerine has high viscosity because of the formation of a networ of hydrogen bonds between the molecules. The networ which extends throughout the liquid ma es the flow difficult.

Effect of temperature on iscosity 5ith rise in temperature, inetic energies of molecules increase. The inter-molecular forces of attraction.therefore.decrease.1ence,li e surface tension, viscosity of a liquid also decreases with rise in temperature. The effect of temperature on viscosity is, however, much greater than on surface tension. !n most cases, the viscosity of a liquid falls by about " percent per degree centigrade rise of temperature. The variation of viscosity with temperature is best expressed by the empirical equation: 0 $ A e1 % 2! 5here " and & are constant for a given liquid,+ is the Gniversal gas constant and T is the temperature on absolute scale.