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    Ternary Systems

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    bhavana

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    © All Rights Reserved
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    sere CHAPTER x THREE-COMPONENT sysTEMs Nature, always working b: , inexorable.—Snmwows 7 *7* 18 alr 8 consistent, always 127. Variance of Ternary §; inci i a 7 ystems.—The principl - lying the interpretation of the equilibria in eee ystems are essentially similar i ee eeety to those described in the cage of According to the Phase Rule the number of d freedom in a three-component system is given by" = -P. When ‘the three components exist in one phase we have P=] and F=4. Hence, the system will not be completely defined unless the four internal variables temperature, total pressure and the concentration of two of the components have been fixed. A three-component system will be invariant (F =0) when five phases co-exist in equilibrium, and the point at which all five are stable together is called a'quintuple point,’ 128. Representation of Ternary Systems.—The variations in concentration of three-component mixtures are conveniently expressed by means of triangular diagrams. The most popular method was introduced by Sir George Stokes and used extensively by Roozeboom. The composition of the ternary mixture is represented by a point within: an equilateral triangle, whose side is made equal to 100 per’ cent and is suitably divided into a number of equal parts. In Fig. 138 (a) the apex A represents the pure component A, ie 100 per cent of A. Mixtures containing 80 per cent’ A will be represented by points on the 80 line drawn parallel to the opposite side, while mixtures containing 60 per cent a e represented on the 60 line, and so on, Similar methods are m2 5 omar. x THREY-COMPONENT SYSTEMS 243 adopted in order-to represent the percentages of B (Fig. 138 (6) and of O (Fig. 138 (c)). If now-we combine the three. diagrams we obtain Fig. 139, which gives a complete representation of the composition of the ternary mixture. Each corner of the triangle represents a —_ 4 ores EL a Fic. 138. Construction of triangular diagram single component or pure substance, A point on the side of the triangle corresponds to a binary system. Thus the point P Tepresents a two-component system containing 40 per cent | 4 and 60 per cent B. A point within the triangle corresponds toa ternary mixture. In any equilateral triangle the sum of ‘the distances of point inside the triangle (as measured by lines drawn parallel to the sides) is a constant and is always equal to the length of the side of the triangle. Thus the point M represents 40% A+ 3 40% B+20% OC. Other methods have also been used for repre- senting teriary systems. Thus, Gibbs employed an equilateral triangle and made the height equal to 100 per cent, while Philip utilised a ight angled isosceles tri- ee Tei entie pur- pose. All these methods ” Af are alike in so far as ¢ the Bpex represents 2 unary, a point on the . sss fees anda point inside the triangle a leas \ 129. Typical ‘Three-Component Sree oe \ components are. gases they will mix eal eee homogeneous system. Such systems connexion with the Phase Rule. ity. go Triangular diagram for three oo ypanents = 244 THE PHASE RULE AND PHASE REACTIONS —omab, When the three oo: ponents are liquids, different types of systems are possible i 4 ring as the liquids are completely chief interest, Petey miscible or partially miscible ‘The “partion However, centres around these liquids which are partially ‘miscible, and o ys ot tie ot ao and such systems may belong to one } Type I. Formation of One Pair of Partially Miscible | Liquids, ‘ype II. Formation Liquids. Type Ir. Formation of Three Pairs of Partially Miscible Liquids, A of Two Pairs of Partially Miscible ¢ Partially Miscible Liquids 130, Type I. Formation of One Pai i is ae e Pair of Partially Miscible eee crannble of this type is furnished by the iene fren) Chloroform, water and wostle acta of ordinary Chloroform and water are only sli i 8 ly slightly soluble in each other, but each can dissolve in all proportions in acetic acid. When, therefore, we gradually add acetic acid to the heterogeneous inix- je"c00" ture of ‘chloroform and water the \ \ ' Two tlauid One liquid pases has mutual solubility of the latter sub- H) stances will be increased, and if sufficient { acetic acid is added, a point will be reached when a ‘single homogeneous liquid phase is produéed, as indicated in Fig. 140. Ce" Actually, the acetic acid distributes itself between the two liquids so that 4 e _ two. conjtigate ‘ternary solutions are in Fia.\140. Miscibility“of ‘equilibrium. © With the addition of Chloroform, Water furthex..--4i7 acid, the compositions of and Avotio Acid ¥:'. 4h»: successive conjugate solutions be- vome mure nexa'iy the same until, finaly, @ poi int is reached which’ the. two: solutions are identical. “At this miscibility * point the mixture forms one homogeneous phase. ‘Lhe Isothermal Equilibrium Diagram. dopting the oe ventional triangular diagram the equilibria at 18° may represented as shown in Fig, 141. When‘chloreform and water 5 THREE-COMPONENT SYSTEMS 24 x dissolves en together, some of the water Be cal noises ate some of the chloroform in the water, in eee wo obtain two liquid layers or solutions, whove son positions are represented by she peer a = ud ie " pe tee now we add a small amount o it will dist itealt between the two layers, and the compositions ot & two jugate solutions will be given by an Haney erie “athe straight line a, joining the two points is called a ti When ii Me tio acid is added we obtain a new pair of temary solutions, whose compositions will be represented by i 1 \0H,.C00H CHCl Le - S H,0 me Fig, 141. Isothermal equilibrium diagram for Chloroform, Water and Acetic Acid the points a, and b,, and so on, With the continued addition and more similar, while the tie-lines become shorter and + shorter, until they finally shrink to a point at K. ‘This point is called the” critical or. plait point.. ‘The curve aKb drawn through the series of miscibility points is called a binodal curve to indicate that there are two related values of the miscibility.. “The tie-lines are not parallel, but slope upwards on the water side, because the aqueous layer dissolves more acetic acid per unit volume than the chloroform layer. For the same reason the critical point K at which the tie-lines shrink to.a point is not at the summit of the curve. The curve aKb represents the boundary between hetero- geneous and homogeneous systems. A point in the region ° outside the. -surye Bgprecents a homogeneous liquid phase Rai of acetic acid the compositions of the two phases become more * © liquid phases, to two layers having the composi ing to the Phase Rule B PHASE RULE AND PHAR REACTIONS side the ourve corre: sponds tn to a heterogeneous put together so that t] re is represented by the point m the relative amounts of th osition of the point on the lin, the two phases in mixtures ee reas but’ the relative volumes of the omar, for example, the ‘three {the composition of the the system will tions a, and bi, reepee ame liquid fe two phases will depend and m’ will be layers, will be oh P+F=C+2, F=5-P, if we keep the temperature and the pressure constant we F=3-P. e, the system exists as one liquid phase it will have two degrees of freedom and will be represented by some point c © B A z ‘7 Fic, 142, The true critical point and retrograde solubility water mixture is of a certain paki add acetic acid to a chloroform] water 1 represented by c’ (Fig. 142) the resulting veer of composition m, will separate into two conj in the region outside the curve aKb. Along the binodal curve there will be two phases, so that a system represented by a point on this curve will be univariant. he True Critical Point—The binodal curve comprises, a series of miscibility or limiting points for systems of different compositions, and it should be noted thatthe true critical point is only realised when the original chloroform] Mm ition. If, for instance, we mixture in the proportion , mixture, say gate layers as x THREE-COMPONENT SYSTEMS 247 described above. In fact, having started with chloroform and Water in the ratio corresponding to ¢’, all ternary mixtures of the series will be represented by points on the straight line c’m0. At M, the miscibility point, the mixture becomes but this does not correspond to the shrinking homogeneous, of the tie-lines to @ point. ‘This occurs onl point K, and i F =3 -P—Identity Restriction, so that F=0. If the experiments are carried out under constant atmos- pheric pressure th e Position of the binodal curve only on the tempe: will depend rature, and the critical point will be perfectly defined for each temperature. In the case of a binary syetexs (p. 100) the critical solution temperature is perfectly defined if the pressure is constant, but both temperature and presser must be kept constant if the ternary critical point is to have a fixed value. ‘The critical solution point of a binary system is indicated in degrées centigrade, but the critical point of a teruary mixture is expressed in. terms of concentration with reference to one particular temperature. y K Retrograde Solubility —Since the critical point does not lie at the summit of the binodal curve, it is possible to change the state of the system above the critical point by simply altering the relative amounts of chloroform and water. It we alter the chloroform|water ratio in the ternary system at w (containing more acetic acid than at K but less than at S), \ the system will traverse the line wz. In this process the system will become heterogeneous at and again homogeneous | at y. ‘This alternation of homogeneity and psec amo called retrograde solubility, and is always observed when the ) criticaf point lies below the summit of the boundary curve. Systems of this type are produced by many ne et mixtures such as water, ether and alcohol, and lead, xin silver. iments are # 11, The Effect of Temperature,—If the experim 248 THE PHASE RULE AND PHASE REACTIONS | CHAP. carried out under constant i tic binodal " stant pressure the position of the binodal .. ae and of the critical point will depend only on the tem- Femture. | The change of composition with temperature may Sanibiceted ee by means of a right prism with the temperature Dinodal ee nt lly.as shown in Fig. 143 (a). In this way the Binodal oe oyetsined at different temperatures form a. mention, °CUPGrY surface. Two cases call for special {"] 1) Ne a hie Ee pe Critical Temperature—A ternary system illustrated in mee Om, ® Teal ternary critical temperature. is ig. 143. The curve akb is the binodal or iso- . c Ara LON, rs (@) Space model + ( Projection on base 1G. 143. No real ternary critical solution temperature Seemsl, mncgp for the three components A, Band C at a ee me {omperature. The curve a,k;6, is the binodal curve binodal wuime system at a higher temperature. The series of nodal curves corresponding to different temperatures sweep out the tent-shaped binodal surface with the summit K in the plane ABBA. As the temperature is raised, the amount of component C in the critical mixture becomes less and less, until, finally, at K, only the two components A and B are present. The curve aKé is therefore the miscibility curve of abe) binary system A/B with the critical solution temperature at K. Such a ternary system does not possess a real critical solution temperature, and this is brought into prominence by projecting the isothermals on to the base of the prism as shown in Fig. 143 (6). Since the component C is absent from the uppermost critical mixture, the point K is simply the

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