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Journal of Crystal Growth 70 (1984) 41—48 North-Holland, Amsterdam

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TWO-DIMENSIONAL NUCLEATION IN A BINARY SYSTEM C. SUBRAMANIAN, R. DHANASEKARAN* and P. RAMASAMY
Crystal Growth Centre, Anna University, Madras-25, India

and Dennis ELWELL
Centerfor Materials Research. Stanford University. Stanford. Ca4fornia 94305. USA

The reversible work required to form a two-dimensional nucleus containing ADP and KDP has been calculated for different values of supersaturations and various values of interfacial tension and these values have been represented by three dimensional prespective plots using computer graphics. The surfaces predict the existence ofthe saddle point nuclei. When a linear dependence ofthe interfacial tension on composition is included, the total number ofmolecules in the nucleus coresponding to the saddle point and the free energy of formation of the nucleus are less than those predicted if it is assumed to that the interfacial tension is independent of composition.

1. Introduction The problem ofnucleation in a binary system is of importance since solid solution crystals are often grown from solution. According to the crystal growth mechanism based on the existence of an adsorbed layer on a crystal face, a centre ofcrystallization generally known as a two-dimensional nucleus must come into existence on the plane surface before thecrystal can continue to grow [1,2]. Expressions for the energy requirement and the critical size oftwo-dimensional nuclei may be derived in a similar manner to those for three-dimensional nucleation. A kinetic approach to the evaluation of the free energy of a 3D nucleus containing two different species, in a binary system was made by Reiss [3]. He used a method similar in many respects to that of Zeldovitch [4] for a one-component system. Shugard et al. [5] calculated the nucleation rate for water and sulphuric acid vapour mixtures for different values of relative humidities and H2S04 vapour activities. In this paper, we attempted to display the free energy surface of the two-dimensional nucleus containing
*

ADP and KDP molecules at 300 K for given values of the supersaturation of ADP and KDP in water. Expressions for the size, the free energy of formation and the total number of molecules in the twodimensional nucleus are calculated, initially assuming the interfacial tension is independent of the composition. But the independence of the interfacial tension on the size and the composition of the nucleus has long been subject to objection. Tolman [6], Defay et al. [7] and Buff [8] suggested that the surface tension of a nucleus should decrease with increasing curvature [9]. Reiss and Shugard [10] considered binary three-dimensional nucleation and calculated the size, mole fraction of the component and the free energy of formation of the nucleus corresponding to the saddle point. In this paper, the problem of the dependence ofinterfacial tension on the composition of a two-dimensional binary nucleus has been treated using the one layer adsorption model based on the Bragg—Williams approximation with empty sites [11].

Presently at Center for Materials Research, Stanford University, Stanford, California 94305, USA.

0022—0248/84/$03.00 © Elsevier Science Publishers B.V. (North-Holland Physics Publishing Division)

30 AG = —aA/lA — bA/lB + 2[lrh(avA + bvB)]112 c. initially assumed to be independent of the A: B ratio in the embryo.389 kT 0 where A/IA is the change in the chemical potential of the species A inside and outside the nucleus. Figs. and increase in the direction indicated by the arrows. is independent of a aiid b. Fig. Subramanian et al. The maximumvalue ofthe free energy is given on the plot and the value of a — 25 erg/cm2.5 and two-dimensional KDP—ADP 5B — 1. 1. The isothermal and isobaric free energy difference between solute molecules in the supersaturated medium and in the nucleus can be written as [12] AG= —aAIIA—bAliB+2lrrha. the nucleus ofKDP molecules. the interfacial tension.and b. (5) .t~ are related to their respective supersaturations by kT ln(~cA/x). (2) In these equations ~A and ~B are supersaturations of A and B components and x is the mole fraction of A in the embryo. The free energy surface for 5A = 1. (1) becomes A/IA = = — . eq. number formation at 300 K with range from ito 20 and 1 to 10 respectively. (3) -~ The surfaces depicted in figs. The free energy surface of KDP—ADP two-dimensional nucleuserg/cm2. a — 25 formation at 300 K with aA — 1. These plots are drawn in such a manner that the viewer appears to be looking down on the surface at a polar angle of 45°from the vertical axis. Classical values of critical size For convenience. (3) in (4) leads to the following results: 0 ‘ (~ ~AG\ )T. 1 to 3 are computer generated three-dimensional perspective plots representing the reversible work AG (in terms of kT) required to form a two-dimensional nucleus containing a molecules of KDP and b molecules of ADP. The necessary conditions for the saddle point are ~AG\ (~a )T.9 and If i. (4) r~ = vAC/A[LA = vBa/A/lB. A/lB kT ln(~~/1 x). 4 and 5 show the two-dimensional plots of AG.42 C. since solid solution crystals are being grown in our laboratory. Replacing the value of r in terms of a and b and VA and VB the respective partial molar volumes. The critical (saddle) point on the free energy surface occurs when the two-dimensional nucleus contains a * molecules of KDP and b* molecules of ADP. (1) b 15. The values of A/IA and zl. A/lB is the corresponding value for B species and r is the interfacial tension. 2.a = 0. the direct substitution of eq. These surfaces correspond to a temperature of 300 K. the two-dimensional nucleus is assumed to be a circular disc ofradius rand constant height h containing a molecules of component A and b molecules of component B.b — 0 a Fig. Here the component A is KDP and the component B is ADP. various values of supersaturations of KDP and ADP and different values of interfacial tension. a.4.4 and a~ 1. / Two-dimensional nucleation in binary system 2. the number ofADP molecules.

to determine how large a correction to the theory is necessary because of the dependence ofinterfacial tension on the composition.C. / Two-dimensional nucleation in binary system 43 15.5 and a — 25 — erg/cm2. a~= 1. This is a simple one layer adsorption model based on the Bragg—Williams approximation with empty sites. A two-dimensional plot of the free-energy AG/kT of the nucleus for different numbers of KDP molecules and up to 8 ADP molecules at 300 K for erg/cm2. a~ 1. The free energy surface for KDP—ADP nucleusfor a — 20 2 (the remaining values are as in fig. (7) .4. One layer adsorption model In the derivation of the values of the critical twodimensional nucleus in the preceding section. 5A = __________________________________________ ~ kT b~2~ 1. so only the interfacial tension between these phases can be measured.389 12 ___ IiI~I Fig. it was assumed that the interfacial tension is independent ofthe composition ofthe nucleus. However the order of magnitude for the correction can be estimated theoretically. 4. We shall be concerned with the effect of change in the number of molecules of each component in the two-dimensional binary nucleus at the saddle point on the interfacial tension in the case of __________ 8 6 6 8 2 6 I 10 12 14 a Fig. erg/cm b Fig. There is no way of measuring the isothermal dependence of interfacial tension on composition. 1). For this purpose use is made of Lundager Madsen’s model [11]. 3. It is impossible. 5. It is only possible to have the two coexisting equilibrium phases in contact. on the basis ofthe existing experimental data.4.5 and a = 25 10 3. a* + b* — = lrhVAo2 (x~vA+ (1 x~)vB)(A/lA)2’ — = = ‘6’ “ ~‘ AG~ irr~htr 1rhvAa~/A/lA lrhvBci2/A/LtB. Subramanian et al. A two-dimensional plot of the free-energy zIG/kT of the nucleus for different numbers of ADP molecules and up to 15 KDP molecules at 300 K for aA = 1.

NAB. Let the energy of an AB pair be + + 24’).b~ + (~+ ~ + 2~”’) Bi n~] (11) NAA~A+ + ~NAB(4A NBB ~ + NLL~ 2p’) + PB + where c is the number ofnearest neighbours. we get — + C ~ + n0 (~A 2 + (EPA + ~B + 2~1)flB n0 ~/2B = e/lA — kT — C n0 — (13) + + 24~I)(’~0 — \‘ ~A no — ‘~)]. NB and NL are the number of adsorbed A molecules. NBB.~ n0 fl n0 — nA no — are the corresponding losses upon the formation of an A-solvent and a B-solvent bond. NAL and NBL respectively. Consider an adsorption layer of binary crystal— solution interface with M adsorption sites in the adlayer in which NA. and also the number of AB pairs. Let PA be the energy of interaction of two molecules of A type on neighbouring sites and 4~ ~ are the and corresponding energy ofBB pair and solvent—solvent pair respectively. NAL and N~~arereplacedbytheirmeanvaluesforallpossible arrangements and using Stirling’s approximation. and ~‘ ~“ ~‘“ = — kTln q~+ kTln t~B c — kTln(1 + — 0) + [2~ ~B + (~A + 2 no 2~~) ~ 24’) ‘~ n 0 — + (~+ + — ~A nBl (10) = ~ — kTIn(1 (~A — 0) + + . A-solvent pairs and B-solvent pairs are NAB.q~and q~ are the partition functions of the single adsorbed molecules. BB pairs and solvent—solvent pairs are NAA. one can calculate [15] the chemical potential of the components as = — + n 0 t2A n + 2~” n0 0 — n~ — n0 nA n0 — + 2~” ~ n0 — n0 (12) kTln q~+ kTln — ktln(1 — 0) The term kTln (1 0) may be eliminated from/lB and ji~by substitution. and differentiating it with respect to nA. while that of an A-solvent pair and a B-solvent pair are ~PA + + 2~”) and + + 2~” respectively. The interface pressure is c ~=-kTln(1-~+ 4A +~NAL(4~A+4~L+24J”) nA+~nB (8) 4iL — 2[ ~A — no 2~’~ n0 n0 n~ + Expressing the canonical partition functionapproxithe adlayer and using the Bragg—Williams [14] of mation. the terms NAA. Here ) is the energy loss upon the formation of an A—B bond. 0 is the fraction of sites occupied and q~. ~ ~ nA (9) The Gibbs—Duhem equation for a three component system at constant temperature is . If the adsorbed molecules are arranged such that the number of AA pairs.44 C. Subramanian et al. / Two-dimensional nucleation in binary system surface nucleation with the solution maintained at constant temperature. ~A and n~ are the number ofadsorbed A and B molecules respectively. the total energy of lateral interactions in the adlayer is [13] E = + + 2~”) n. NBB and NLL respectively. n0 is the number of sites per unit area. NLL. B molecules and solvent molecules respectively and M> NA + NB + NL.

(13).C. (21) and (24). From eqs. (15) The equilibrium concentration oftwo-dimensional nuclei containing a molecules of KDP and b molecules of ADP is related to the free energy of formation of a two-dimensional nucleus by [12. 8n~ 0 a/IA n0—n~—n~ aflA n 4. (16) a/IA kT(n 0 — nIL) — + aflA nA(nO — nA ~B) 2c~” n0 mers. / Two-dimensional nucleation in binary system 45 NA d/IA + NB d/IB + NL d/IL = M d~. but strictly speaking it is a function of AG. b) + ~ b n(a. (20). The total number of adsorbed molecules may be related to cluster size and concentration as ~ The surface supersaturation of the A component ~ can be expressed as PA° + kt In /3~. (20) and ~/IB Similarly 1”2 0(avA + bvB) 1/2 VB + (irh) + 2[lrh(avA + bvB)]1”2p(nA + nB) x{kT n0 — ackT aflB — n 0 C [2~”nB + nA(~ — + p’)]. (14) which yields a/IL Eqs. (21) — C n0 [2~” 1A ‘ +flA(~ — + — ~‘)]}= 0. b (23) (17) Our theoretical estimates are not much affected ifwe assume that anA aflB = — — kT a ln /~ kT 1 = ~A + — 1 ~O ‘~A — — 2c~” kTn0 18) anA ~J3 The Gibbs adsorption equation at constant temperature for unit area of interface can be written as [17. (4). Subramanian et al. (24) aa ab Here p is assumed to be a constant. (25) [2~”nA + nB(4) — ~‘ + p”)].18] aa = nA + a/LA anA + n}3 a/LB anA anA (n — — a/IL (19) p(nA + nB). Compositional dependence of interfacial tension — n0 n0 — a/LB ~ anA n~ — nIL + — a c2~ 1~A — ~B . (16). they are 1 c(avA + bvB) 1/2 VA /IA + (7th) 2[lrh(avA + bvB)]”2 p(nA + flB) p(nA + nB). n~ ~ ~A — — kT n 0 — C no [2~”nA+ nB(~ — + anA — n0—n~—n~ C ~“)]}= 0. (26) no . (20) and (21) give the variation of interfacial tension with respect to the number of adsorbed A and B type molecules respectively. (18) and (19). The necessary conditions for the saddle point including the dependence of interfacial tension on the composition can be found from eqs. The value of ln /3~ given by [16] is /IA = + ~B = a a n(a. — 0 nA nB) ônA . = + x ~kT 1. (3). b).19] n(a. b) = n’ exp( AG/kT) (22) where n’ is the initial concentration of the mono— Substituting the values of a/IB/anA and a/IL anA = a~/anA.

6 4G*/kT 232.4 1.7 1.6333 0. (28) — — The numerical values of the “classical” results and the corrected values are presented in tables 1 and 2.7 481.6 505.4814 0.6 179.)].6 1. the value of (a* + b*) is less than that given if a is independent ofa and b.5 1.6 519.6071 0.0 186.1 1.” ~~4.9 567.5 0. (25) and (26) vanish to give the classical values (section 2). To compare the results obtained from the classical theory and our values.7 586. the last terms in the eqs.4285 0.9 1.3 533.5291 0. — — 4.’ = 24.3928 0. Table 1 Calculated values of critical nucleus parameters for x~ 1.1 533.1 1.6 213. Table 2 gives values for C~A= 1.5344 0.3 1.4989 0.5 199.’.5 1.3 471.5 1.4666 0.5172 0. 971 788 661 570 500 719 612 533 472 424 570 500 446 403 368 472 424 385 353 325 (a* + b*) 29 25 22 20 19 24 21 19 17 16 21 19 17 15 14 18 16 15 13 12 AG~/kT 765.5769 0.7 1. no = 4 x 1014 cm 2 (square lattice where each site is 5 x 5 A2.5004 (a* + b*).1 1.3548 u.5483 0.5 0.5 193.5 1.7 1.5015 0.5kT a/n kT = 25 —‘ — = — — In A — 2r 7trsui~a L a .” = 24. The total number of molecules in the binary twodimensional nucleus corresponding to the saddle point are calculated by solving the eqs. 4. and various values of a~and a~ xk 0. Subramanian et al.4 185. (25) and (26) ln 1 x’~’ — ~ The free energy of formation of a two-dimensional nucleus is aa AG * = [irhv(a * + b*)]lh’2 [a 2x* aa aa + (1 X *) (a* + b*)].3 165.’.476 0.5kT and a/n0lcT — 25.” and 4.” = 0.5416 0. Table 1 presents the values for 4.0 203.5 160.” and (27) a.5 443. It is shown that the value cn kT [(~A + ~~)(4.*\11/2 B 0 and various values ofsupersaturations.9 186.8 689.3 1.1 1.5757 0.4400 0.9 and c~= 1.4 549.1 493.6 505.7 1.9 607.5277 0.1 A.5 172.4937 0. This assumption will not seriously affect the numerical analysis since the experimental value of VA/VB for KDP/ADP is 0.7 and various values of a/n0kT and 4.9 167.1 * U L.1 198.0 .9 0.46 C.1 1.3939 0.6 631.4935 0.9 586.5047 0.535 0.0 175.6 658. we assume VA = VB = v as in the regular solution model.3 1. / Two-dimensional nucleation in binary system If the interfacial tension is independent of the composition.8909.4663 0.3 150.5 0.5104 0.4835 0.5 0.4687 0.1 216.9 461.4871 ~‘ — 0. Our theoretical estimate yields the result that for the given values of 4.4 549. v 10 23 cm3/molecule and h = 3.3 1.8 188.4594 0.518 0.9 1.0 174. For this numerical analysis we have used the following values: c = 4.” — — 4.9 1.4333 0.7 2.1 157.5118 0.”) x (~B — ~A) 2(~4.4943 0..4832 0.

5kT 25 50 100 200 25 50 100 200 25 50 100 200 0. Expressions for the critical values of the two-dimensional binary nucleus corresponding to the saddle pomt are presented for the case where interfacial tension is independent of the composition and size of the nucleus.4 1587 4695 184.5277 0. The mole fraction of KDP in the critical nucleus is not only defined by the supersaturations of KDP and ADP as given by the classical result but also depends on the energies of the interaction between the adsorbed molecules due to the dependence of a on a and b. Conclusion The free energy surfaces of the two-dimensional nucleus containing KDP and ADP molecules at 300 K for the supersaturations of ~KDP = 1.IG*/kT 160..5954 0.4891 0.5kT of x *. the total number of molecules and the free energy of formation of a two-dimensional nucleus corresponding to the saddle point are less than those predicted if a is independent of the cornposition.5277 0.C.5277 0.5 and 2 and a = 20 1. Using eq.4714 0. and various values of ~‘ and a/n = a/n0lcT —0.1 527. In spite ofthese approximations this model gives useful data on how the total number of molecules and the critical free affected by the dependimensional binary nucleus is energy of the twodence of interfacial tension on the composition depending on the energy loss on the formation ofnew bonds.6 1743 5185 AG~/kT 471.5277 0. but also by the energy of interaction between the adsorbed molecules. is not only determined by the supersaturations of ADP and KDP.4466 0. that is.5277 0.5277 0. Madras.9 1470 4332 171.4 490. When the dependence of iterfacial tension on composition is included using the Bragg—Williams approximations with empty sites. Subramanian et a!.3 1885 7542 30160 471.7.5277 0. These surfaces show the existence ofthe saddle point in the system considered.5277 0. 5.5277 0. (28) we calculated the value of the free energy required to form a twodimensional binary nucleus corresponding to the saddle point including the dependence of interfacial tension on the number of molecules of each component in the nucleus.4 with water and a = 25 erg/cm ~ADP = erg/cm2 have been plotted three-dimensionally as perspective plots using computer graphics.3 1885 7542 30160 471.5277 0.6250 (a* + h*)~ 368 1471 5887 23550 368 1471 5887 23550 368 1471 5887 23550 (a* + h*) 14 30 63 132 16 36 76 159 20 44 95 200 0lcT .5741 0. / Two-dimensional nucleation in binary system 47 Table 2 Numerical values of critical nucleus parameters for c~ 1. for his help in getting the . the model has another limitation. the mole fraction of A in the two-dimensional nucleus corresponding to the saddle point.3 1885 7542 30160 0 0.9 and a~— 1.5590 0.5015 0.5277 0.5277 0. Acknowledgements The authors would like to thank Dr. Apart from this. Our numerical results show that the reversible work required to form a nucleus is less in the case ofincluding that effect for the given values of the interaction energies between the adsorbed molecules and interfacial tension.5277 0.5277 0. In the model of one layer adsorption considered here. Shanker of Anna University.5277 0. only the nearest neighbour interactions are treated and the adsorbed molecules are distributed randomly in the adlayer.5277 0.8 612. it is a localized layer model in which the adsorbed molecules occupy one site each.

Subramanian et al. Lundager Madsen. Modeling Crystal Growth Rates from Solution (Prentice-Hall.C. Vol. in Surface and Colloid Science. 110] H. J. Crystal Res. Ed. J. Crystal Growth 46 (1979) 495.48 C. Ohara and R. Dhanasekaran and P. 16 (1981) 863. Buff. I. 18 (1950) 840. London. Englewood Cliffs. D (Appl. Chem. NJ. [12] R. New York. J.V. Phys. Phys. Ramasamy. 1969). Surface Tension and Adsorption (Wiley. Shugard. Tolman. Phys. Chem.P. Phys. Zeldovitch. E. J. J.) 15 (1982) 1047. . J. Technol. Dhanasekaran and P. Reading. Dhanasekaran and P. computer graphics. 83(1981) 623. Defay. R. Ramasamy. Chem. Technol. [2] M. A. 65(1976) 5280. Hill. Reiss. 1973). Reiss and M. Introduction to Statistical Mechanics (AddisonWesley.C. Reid. Phys. [5] W. 16 (1974) 5298.H.W. Dhanasekaran and P.) is grateful to the authorities of the Indo-American Fellowship Program. Phys.J. [91F. [15] R. [171 R. 17 (1949) 333. Phys. Reiss. References [1] J. 1. J. Crystal Growth 66 (1984) 380. Chem. J. 16 (1981) 641. [16] R. Technol. Ramasamy.E. [14] T. Zh. MA.H. 81(1981) 543. 1972). Mullin. Colloid Interface Sci. Chem. J. New York. Dhanasekaran and P. [4] J. Everett. Temkin and V. Shevelev. Fiz. Crystallisation (Butterworths. Bellemans and D. 23(1955) 419. 1966). [7] R. J. Heist and H. 1960). Crystal Res.C. Ill] HE. Crystal Res. Eksperim. [6] R. Shugard.A. Prigogine. 12 (1942) 525. 16 (1981) 299. Matijevic (Wiley. [3] H. One of the authors (R. Ramasamy. [18] R. / Two-dimensional nucleation in binary system Goodrich. Teor. Dhanasekaran and P.D. [8] F. [13] R. Ramasamy. Colloid Interface Sci. [19] D. Ramasamy.