ichap.2] Jen 2) Liquips 57 ss (i). Dunstén (1909) discovered a useful relationship between viscosity and inverse molar volume. The relationship is d M *% 1x 10% = 40 to 60 where d is the density and M is the molecular mass of the liquid. This relationship is true only for nonce (normal) liquids, where’ as for associated liquids the value is much- greater than 60. This relationship is very useful in deciding whether a given liquid is associated or not. (In CGS units, the multiplication factor is 10° but in SI units it is reduced to 10). Table 2.4: Normal and associated Liquids according to Dunsten. Liquid State ¢ x n x 10° Benzene Normal liquid 73 Acetone Normal liquid 43 ‘Toluene Normal liquid 56 Water Associated liquid 559 Glycol Associated liquid 2780 Glycerol Associated liquid 116400 (ii) Molecular Structure Effects the Viscosity of Liquids. A spherical shaped molecule offers least resistance to flow. The shorter the chain length of a molecule, the lower will be its viscosity coefficient. n-isomers have usually greater viscosity than branched chain isomers. The viscosity of a trans-isomer is greater than cis-isomer. (iv). Intermotecular forces. ‘The stronger the intermolecular forces in the liquid, the greater will be its viscosity. H,O and CH; OH molecules are about the same size, but the viscosity of HO is greater due to presence of strong hydrogen bonding which makes the-flow more difficult. ' (v) Rheochor. |Newton Friend(1943) showed that if the molar volume (M/d) is multiplied by the eighth root of the coefficient of viscosity, a constant value is obtained which: is known as Rheochor, M i R= qxné .. (24) The Rheochor R may be defiried as the molar volume of the liquid at the temperature at which ite viscosity is unity. Like parachor, rheochor is both additive and constitutive. It chould-be noted that the rheochor is less useful for determining chemical structures than parachor. * 7 ‘Scanned with CamScanner~ OK OF PHYSICAL el ATEXT BO HEH Applications of Viscosity Measurement tions have BEER USE Yo deen x sol aa, A Ine 1. The viscosity measurements of polyme! tween intrinsic viscosity [q] ang pi* molecular mass of polymers. The relationship betw eye mass of a polymer is ink equation) (Mark - Houwink eq 4 m1 2 a limiting viscosity ny . on : iscosity which is the limiting imber y ere [n ] is the intrinsic viscosity roaches,20r0. k and a are gy "Mt concentration of the polymer in a given solvent app: Il as the solute. Factor aig oat Parameters depending on the nature of the solvent a8 ie alee 5 shape factor. For a randomly coiled molecule a= 0. ee hold well for @ given pai spherically coiled molecule a = 0. The relation seems er ag solvent when Mexceeds 30kg mol. , . lee ang 2. The viscosity measurements are applied for controlling the manufacture of Pring rubber, glue and synthetic polymers 3. _ This study is also of great significance for the solution of many technical problems, example, the amount of energy required for stirring of a liquid, mixing of liquids, matig slurry or sending of a liquid through a pipe depends directly on the viscosity. 4 _ For pumping the crude mineral oil and natural gas from one place to another regi the viscosity measurement so that a suitable pressure is applied for their transportation, 5. . Lubricants are graded according to their viscosities. 6. ‘The viscosity of a liquid or solution reduces the rate of oxidation at the liquid surfay, since the increased viscosity makes access to air more difficult. 1. Viscosities of lubricating oils used in machine play an important role, 2.7 REFRACTIVE INDEX "Refractive index (n) of a transparent. substance is defined as the ratio of tk velocity of light in vacuum to the velocity of light in the given medium". The refractive ina of any substance depends upon, the nature of. substance, temperature and the wave lengthd, light used. Whenever a beam of monochromatic light passes from one medium into the other, it suffers a change in the direction of propagation, This change of direction is called refraction, depends on the nature (refractive index) of the two media, and the direction in which the light travels, . When a ray of light passes from a rarer (air) to a denser medium (liquid or glass), it bends towards the normal atthe point of incidence, as shown in Fig.2.14, According to Snell's law, the ratio of the sine of angle of incidence and that of refraction is constant and characteristic for that medium. ‘Scanned with CamScannerchap.2] Liquips . a) sini . = Sing (Snell's law) v= (26) According to the wave theory of light, the ratio of the sines of the angles of incidence and.refraction is identical with the ratio of the velocities of light in the two media. Thus _ sini velocity in air n= SS) = —eccity mar sinr velocity in liquid “ren According to the law of refraction, sini _ tty sinr = hy ~ (28) where n; is the refractive index of the rarer and nz the refractive index of ‘the denser medium. As the angle of incidence increases the angle of refraction also increases. When i= 90, r reaches its maximum value and is known as the critical angle. Since sin 90 = 1, : ny Eq.(28) becomes sinr = 7 (29) 2 If the angle of incidence is greater than 90, the ray is totally reflected. Most of the refractometers work on the principle of critical angle for measuring refractive index of a medium. Measurement of Refractive Index ‘The refractive indices of liquids can be measured directly with calibrated instrument called refractometer . In practice, Abbe and Pulfrich refractometers are commonly used. (i) Abbe Refratometer. A general sketch of the Abbe refractometer is shown in Fig.2.15:, the optical system of the Abbe refractometer consists of three parts (1) a mirror M, (2) two prisms A and B housed in a box hinged at H and (3) a fixed telescope T and an eye-piece O. The two prism faces can be held in contact with knob C . To the box carrying the prisms , is attached an arm R which moves along a graduated scale S, a direct reading on the scale gives the refractive index . Procedure. The prism box is opened , a drop of the test liquid is placed between the two prisms and then the box is closed. The cross-wires of thi telescope are focused by rotating the eye-piece and the mirror is adjusted for maximum illumination. The prism box is slowly moved backwards and forwards by means of the knob C until the field of view becomes partly dark and partly bright. When the white light is used the coloured fringes observed are removed by rotating the " compensator " ( consisting of two prims attached at the nose of the telescope ) and a sharp line will divide the bright and dark portions. The prisms box is then rotated until the .end of the bright portion coincides with point of ~ Fig.2.15. Abbe Refractometer. ‘Scanned with CamScannerA TEXT BOOK OF PHYSICAL Chega, refractive index is direct intersection of th vires of the teleSeoP° and the Y Roteg section of the cross- the scale through the eye piece ic mperature and wavelength of light, In ffected by the Be wavelenst?s prisms A and B are eng seure ant 7 light is preferably used . Since refractive index is af hy order to maintain consistency of temP® m in a water jacket J and sodium or mercury Gi) Pulfrich Refractometer. Pelitich refractometer is very accurate and simple 10 principlé «or measuring the refractive Light A* indices of Nyuids. The basic design of the instrument ffs shown in Fig(2.16) - The essential pfft of the instrument is a right angled glafts priem with a small glas® cell cemented to its top. “he liquid tocbe examined if placed in the glass cell and beam of monochromatic light is made to enter at ‘grazing incidence, along the éurface between the liquid and the prism. It follows the path ABCD and i& Telescope Fig.2.16. Pulfrich Refractometer, bserved by'a telescope at D. If r be the angle of refraction wher’ the angle of incidenes a. : ; nro 90° , then. sinr=7, where n, is the refractive index of the liquid and ny that of the glass prism. It is clear form | Fig.(2.14) that sin sin (90—r) =cos r, thus we have’ =m oo sr FS ~ ny cos, but sinr = Vi=cos'% (a trigonometric relation) La Substitujing the valle of cos r from Eq.(31) into Eq,(32), we get , { “a oa ; wine 4 [poe oafSee . ry a ng Ot) te Festive index ng’ of th prism is known and the angle i is measured reactive index of the liquid, ean be taleilated. In practice tables of values «m= 8 ferent xplues of iia also supplied with the instrument. aie F a ‘Scanned with CamScannerschap.2) “Liquips: 6 Refractive Index and Composition The refractive index of a liquid varies with the wavelength and also with the temperature. To eliminate the effect of temperature, Lorentz and Lorenz (1880) derived a relationship between refractive index and density of a liquid. . n?-1 1 wea’ id -» (35) R where R is a specific refraction or refractivity, which is independent of temperature, n is | the refractive index and d the density of the liquid. For comparison, molar refraction or molar refractivity R,, is employed which is equal to the product of specific refraction and n-1 M ’ R m+2*d Loy - G8) molecular mass, i.e., ‘The molar refraction like specific refraction is temperature-independent, but depends upon the wavelength of the light used for measuring the refractive index.'It is for this reason that the molar refractions are generally reported for a definite wavelength e.g.,a~, B-. or y- lines of hydrogen or sodium D — line. : Since refractive index is dimensionless, the units of molar refsection-are the units of M/d, ie., volume expressed in cubic meter per mole (m® mot), The molar refraction is an additive and constitutive property. The molar refraction of a molecule can thus be considered ' to be a sum of refractions of the atoms and bond existing in the molecule. Table 2.5: Molar refractions (cm* mol!) for some atoms and bonds for D = line (Vogel 1948). . a Atom Rp Atom Rp Bond * Rp Hydrogen 1.028 | Chlorine 5,844 | Double 1575 ‘| ' Carbon 2.591 | Bromine 8741 | Triple” 1.977. Oxygen 1.764 | Iodine 13.954| 6-Cring 0.157 > C=Ogroup 9.010 | CHpincreiment 4.617 4Cring - 0317 5-C ring -0.10 | Methylradical 5.653 |” is. —OH group 1.518 | Ethylradical 10.300 Ethers(Q) _1.643_ | - COOH 7.227 Ein Molar Refraction and Chemical constitution oe (i) ‘The average difference of inolar refraction. betwaen two consecutive members of a Homologous series of esters and alcohols for a CH group is 4.606 10° and 4,634x 10% respectively: . (i) Deciding constitution. The determination of molar refraction helps us to decide the structure of a molecule. For example, the experimental molar refractiop value for benzene is 25.93 which is in agreement with the calculated value 25.289, and thus . ‘Scanned with CamScanner62 A TEXT BOOK OF PHYSICAL CHEMIST, Supports the Kekule’s formula for benzene. Wl 6c 6x 2.591. = 15.546 Hy Once A SH o 6x 1,028 = 6.168 f tl 3 double bonds ... 3 x 1.575 4.725 AY a k =-0.15 H ‘NS i f 2 Table 2.6: Refractive indices and Molar refractions (m3 mor!) of some compounds at 20°C. one 6-membered ring Compound R® (or D-line (m? mol) « Acetone 13571 1.615 x 107° Benzene 1.5010 2.618 x 1075 Acetic acid 1.3715 1.330 x 10-* Carbon tetrachloride 1.4573 2.651 x 107% Chloroform 1.4426 2.125 x 10-5 Ethanol 1.3600 1.278 x 10-5 Toluene 1.4969 3.092 x 10-5 Water 1.3928 0.375 «10-5 Example2.2. The refractive index of carbon tetrachloride at 20°C is 1.4573. Calculate ix molar refraction if its density is 1595 kg m=. Solution. n= 14573, d= 1595 kgm™"$', M= 154x10% kg mol", R, =? (1.4573? -1 154 x 10-$ kg mol"! Using — 1 M_ (0.4573) 5 ¢ mol m+2 * d ~ (145737 +2 * 1595 ke mol? = 2.651 x 10° m3 mol~! Gif) Optical Exaltation. A compound containing conjugated double bonds (C= C- C=C) has a higher observed molar refraction, R, than that calculated from atomic and bend refractions. The molar refraction is thus said to be exalted (raised) by thé presence of conjugated double bond and this abnormality is called optical exalatation or optical anomaly. Table 2.7: Some examples of Optical Exalation. Formula of isomers | Observed R,, Calculated Ry AR. CHy-CH=CH-CH=CH-CH, | 2.987%10° | 2678x10% | +0,109+10"! CH, = CH ~ CH = CH-CH=CHy| 3.05810 | 2.852% 107 | +0.206« 107 ‘Scanned with CamScannerjcnap2)_ Liquips 63 If the conjugation occurs in the closed rings as in benzene, the optical exaltation disappears. However, if the conjugation occurs partly in ring and partly in side chain, optical exaltation is observed, e.g., styrene and acetophenone show optical anomaly. 0 W — C-CH, — CH=CH, Styrene ‘Acetophenone ‘This phenomenon may be due to the interaction of the delocalized electrons with the electromagnetic radiation. Molar refraction of the Solution: The molar refraction ‘Ra’ of the solution is given by -1 (qutaas) d where 'x;' and 'x, "are the mole fractions of the solvent and solute, 'M,' and 'M,' are the molar Rs nee2 masses of solvent and solute respectively. Refrachor. Joshi and Tuli (1951) introduced a new physical constant known as refrachor. It is denoted by F and is expressed as [F] = ~ [P]log @-1) BD In addition to the usual application of parachor, refrachor has‘been found quite useful for, (@ determining the composition of keto-enol mixture. (i) _ studying the structural isomeric compounds. (iii) distinguishing between stably-linked and reactive halogen atoms. 28 DIPOLE MOMENT ‘The separation of charge in a polar covalent bond creates a dipole, The word dipole means "two poles" and refers to the positive and negative poles or ends, the result is the separation of charge within the molecule. ‘The polarity of a molecule is expressed quantitatively by its dipole moment, » Greek letter mu), which is a measure of the magnitude of the separated charges and the distance between them. The dipole moment, 1, is defined as the product of the magnitude of the electrical charge and the distance separating charges of equal magnitude and opposite sign. Thus © ‘Scanned with CamScanner~ 7 64 A TEXTBOOK OF PHYSICAL CHEMISTay HOE qxr ww (38) The dipole moment is a vector quantity and is represented by an arrow showing the direction from positive to the negative end of rar the dipole. The length of the arrow represents Fi Dipole moment and its the magnitude of dipole moment. igh vector representation, A litter molecule A triangular molecule © Fig.2.18 :Vector Addition of Dipole Moment For a polyatomic molecule containing two or more bonds, the net dipole moment is vectorial sum of the individual bond moments. In a linear molecule, the individual bong moments may exactly cancel each other on vector addition and dipole moment would be zero, _ Units. In SI units, the charge is measured in coulombs and distance in meters. For an electronic charge = 1,602 x 10-!°C (= 4.8 x 10~esu) and distance 10-!° m(=1 A‘) Dipole moment = Electronic charge x distance : = (1.602 x 10-C) (1x 107m) = 1.6@2x 10-®Cm In honour of Peter Debye, who developed the theory of dipole moments, the unit Debye is used. . 1Debye(D) = 10-" esu cm = 3,336 x 10-*? Cm Table 2.8. Dipole moments of some molecules in Debye units. Dipole moment Dipole moment Molecule Debyes) Molecule x Debyes) HF 1.80 NH, 147 HCl 1.08 PH, 0.55 6 HBr 0.79 CH,C1 1.85 HI 0.38 cl, 0.0 ' HO 1.82 cH, 0.0 | HS 1.10 CH, 0.0 : | CHC, 115 Hy 0.0 | .C,H,OH 170 CO, 0.0 C,H,OH 1.70 SO, 1.60 : CH,OH LT CH, 0.0 . ‘Scanned with CamScanner