BULLETIN OF THE 133 KOREAN CHEMICAL SOCIETY VOLUME 3, NUMBER 4, DECEMBER 30, 1982 Viscosity and Thermodynamic Properties of Liquid Sulfur ‘Man Chai Chang and Mu Shik Jhon’ Department of Chemistry Korea Advanced Instituto of Science and Technology P.0. Box 160, Chengyangni Seoul 181, Korea (Received April 10, 1982) thas been presumed that the molten sulfur above 159°C consist of an equilibrium mixtu eof Sings and S, polymers where ‘the number average degre of polymerization, P, islarge.But itis known thet admixture of halogens with liquid sulfur greatly ‘reduce the viscosity. Constructing anew equilibrium equation itis posible to evaluate the viscosity when halogens are added to liquid sulfur. Calculated viscosity is in good agreement with experimental values. Using the proposed model, the thermody namic properties of liquid sulfur are also caleulated over a wide range of temperature which the sulfur exists asthe polymer. Introduction Fanelli! obtained the temperature variation on the visco- sity when various concentration of halogens are added to liquid sulfur, which brought out the enormous modifying effect of these elements on the viscosity of liquid sulfur. He also indicates that, with each increment in the concentration of halogens, the viscosity becomes smaller. In equilibrium polymerization reaction, halogens absorb the radicals and terminate the polymerization, therefore the viscosity is re- duced. ‘We evaluate the viscosity of liquid sulfur containing halo- ‘gens by using a new equilibrium equation in which assumed that halogens, Ss rings, and Sy chains are in equilibrium each other? ‘The partition function of liquid sulfur is obtained as the product of conventional partition function for the liquid and the configurational one for the Z-transition® which uses the simplified expression for Bragg-Williams approximation of order-disorder phase transition, Using this partition function, the thermodynamic properties of liquid sulfur can be cal- culated. ‘The results of the viscosity of liquid sulfur containing ha. logens and thermodynamic properties of liquid sulfur are in ‘good agreement with the experimental data ‘Theory 1, Viscosity of Liquid Sulfur Contatiaing Halogens When halogens are added, the equilibrium polymerization Of liquid sulfur can be represented as follows? Initiation K=(M*)/ (M1) (wr) =K a Propagation and termination LP Mt 5 Ky= (MD) (at) Ky (Mf) (M*) (MN) KM) @) o Symbolically we designate Sy ring as M, S$ chain as M*, ‘and Q as halogen, respectively. The total concentration of polymer molecules, N’, and the total concentration of Ss ‘unit in the polymer, W’, can be represented as follows Mt ME tM} MQ EMO E MIG bo K(M)/{1-Ky(M)} +K' @K(MD/{1-Ke(M)} =K(M) (14K @}/(1-Ks0} o 4 2MEL3ME+ = + M*Q42MI0+3M 104 (M) / 1-KQD}+K' (Q)K(M) | (1 KM}? =K(M) +R @}/0-K}? o When halogens are added, the number average degree of polymerization, P', can be obtained from eqs. (4) and (5). w Pes (W)/ WV) =1/ 1-Ka) o Here, the number average degree of polymerization, P’, has the relation with the viscosity such that?134 Bulletin of Korean Chemical Society Vol. 9, No, 4. 1982 ( ‘where 7 and 7 are the viscosity of sulfur containing halogens and pure sulfur, respectively, and WY means the concentra- tion of polymers ‘The quantities (Ma) and (Q3) which are the initial concen- tration of S,{ring) and halogen, respectively, are expressed by a (My =) +0) = QD +K AD (14K Q)}/ 11K OO? ()+KGD K'@) (1K) @+a") @+KD (1+K' @)}/ 1K) =@+KQDK’ @/(1-K} o In eq, @), to calculate the equilibrium constant, K’, we introduce @ new equilibrium such that ® Q) QM = MQ (10) Where Q- represents the halogen radical {In eq. (2), we assumed that all the equilibrium constants in the polymerization reactions are same as Ks, 0 itis possible {0 represent the equilibrium constant in eq, (10) as approxi- mately aks, ‘Where the halogens such as chlorine, bromine, and iodine, are differ in activity to attack a sulfur ring, and the notation ‘a means the activity of halogens to attack a sulfur ring. Therefore in above equation, M*Q is represented by (4t*Q) =aK(Q-) (1) an ‘Thus K’ in eq. (3) is represented as follows K'=(M"Q)/() (Q) =aky(M) (Q-)/(M*) (Q) thy(M) (Q-)/K(M) (Q) =aKe/K-(Q-)/@ a-Ko:Ky/K SAVKyIK (2 (by eg. 10) In eq. (12), Ko represents the equilibrium constant where the radical of halogen is produced, and we replace akg by A. 2. The Significant Structure Theory of Liquids!" According to the significant structure theory of liquids, liquids have quasi-lattice structures ike solids and the lattice points are occupied by molecules or fluidized vacancies of molecular size randomely distributed throughout the quasi~ lattice. The fluidized vacancies provide gas-like translational dogrees of frecdom on the vibrational degrees of freedom of, neighboring molecules because the molecules can jump into them, The fraction (V-V,)/V of the degrees of freedom are gas-like and the remaining fraction V/V can be thought of as being solid-tike where V and V, indicate molar volume and solid-Iike motar volume, respectively. Thus, one mole of liquid can be considered as if it were made of N(V-V)/V_ sg2s-ike molecules and NV,/V solid-like molecules where is the Avogadro number. In view of this, the partition function, fy, for a mole of liquid can be written as Man Chai Chang and Mu Shik Jhon fun ph pr ay The sold-tike partition function {f, is the usual partition function for a solid multiplied by the positional degeneracy factor I-+nsexp(—ex/RT), because the fluidized vacancies confer the additional site yexp(—ey/R7) to a solid-like mole- cull, Here, ny and c, can be written as nan aay and. as, Where E, is the energy of sublimation of the solid-like ‘molecules and 2 and n are the proportionality constants Which will be evaluated. (Once the partition function is given, thermodynamic quan- tities of the liquid can be obtained from the partition function 3, Partition Function of Liguld Sulfur The partition function of liquid sulfur is written as. FuFoae fant a6, Here fig is the conventional liquid partition function which can be obtained by applying the significant liquid structure theory to liquid sulfur. f.41 is the configurational partition function which is introduced to account for the thermody- namic properties accompanied by the Z-transition, For the configurational partition function, we use the Bragg-Williams approximation which explains the nature of A-transition, 1. Conventional Partition Funetion. According 10 the sig- nificant structure theory, the partition function for a mole of liquid, fy, i8 given by Seah $, an For the solid-like partition function, we have assumed that there are two structural species in equilibrium. Sstring) = S3(diradical) ‘The equilibrium constant X is writen as Keai(diradical) jxg( ring) =f.4/f., exp ( 4H TAS PAV a AH=32,800caljmole, and 48=23 bere 4V=V,,— Vip, cal/deg, mole" ‘Thus, the partition function, fs is Daft fife K (9) ‘Where x and x* are the mole fration of Si¢ GiradicaD, respectively, with the relation x-+2*=1, and the Sdsing)-tike partition function can be written as exp(E,/RT)_, Scary eatsViscosity and Thormodynamic Propertios of Liquid Sulfur aE,V, fla-emven) weir) la-emen> en From a mass spectrometric study,!? the vapor of liquid sulfur is composed of many species such that $4 ring, S; ring, S6 ring, and S molecules. Then the gas-like partition function, f, is waitten as onl LPS GLY an Where x27 2% and 2, ate the mole fraction of Sy ring, 'S; ting, Se ring, and S, molecules, respectively, with the relation ayhapbaghn=l. ‘Thus gas-like partition function, f, is composed of its various composition" as follows, Fe FE LLY G INET 2 Where the translational, rotational, and vibrational partition function are given as (QamkT)*2 | eV BERT) oY en . BE BPABON ATI (Gop three dimersional) fre Ser (for two dimersional) (24) F0 = [-exp(—ae/ AT) es, Where the symbols have their usual statistical-mechanical signiticance. In gaseous state, molecules are in relation with ‘each other as follows? Sutring) == Sfving), Ky=ecing)/zacing) (26) Soring) = Setting), Ke=xuting)/2y(ring) 27) Sy(ring) Zs S(cing), Kr=-lcing)/xd(ring) (28) Here S, molecules are regarded as 2-membered ring and Ky, Ko, and K; can be calculated, and its method is listed in “Appendix I. The values of sri, 23, and 2 are tempera ture dependent. In the calculations, V, and E, are given by AVEERY, 9) LA Ey tet Ey tt Ey tet Ents 0) where Vand V; are soli-like volume of S,(chain), and Si(ciog) respectively. ‘And E,y Ey Eyy and E,, are the sublimation energy of Sitting, solid)>Scng, gas), Sing, solid)=>S4Cing, 62), Sutring, solid)>>Sitring, 25), and Sdcing, solid)=>Sxgas) transition, respectively, and the way of obtaining a sublima- tion energy are introduced in Appendix I. 2. Confieurational Partition Function. The configurational partition function is derived by the Bragg-Williams approximation. The configurational partition function is siven by the following equations: Sant = WOO) -exp{—E(O) [AT ay Bulletin of Korean Chemiol Society, Vol. 9. No. 4, 1982 135 MO NO -EITT ROY on 2 z EO =N VAN VAN (Vi VIEL V IO =v 63) Here, 0 isthe long-range order parameter; Nand N~ are ‘the numbers of spins in the up and down directions, respec- tively. 17(@) is the number of possible ways of obtaining the Nj state of spins; £(0)is the configurational internal energy Of the system; V. and V_ are potential energy of the up and down directional spins; respectively; Vo is the energy of the completely disordered state 0=0; V_—V,=Vol is assumed, The order parameter 9 is obtained from = Ty tanh (Sea) os Resuts And Discussions 1, Viscosity of Liquid Sulfur Containing Halogens Hilogens reduce the viscosity of sulfur above 160°C through the chemical reaction with the sulfur shown in eqs. (2) and (3). ‘And, the following reaction can be considered as ‘Se(chain) +53 (chain) === Sf,(chain), (6.g=1.2,3, 007) 69) Where equilibeium constant Ks can be represented as follows (Sp) (82) (83) (S589) ‘Here we assumed that all the equilibrium constants in the polymerization reactions are same as Ky, and the equilibrium ‘constant K; in the radical-radical reaction can be written, as Ky/K without considering the effect of chain length. Now, we consider the following reaction (3) = Ky Gi K =Ky a9) Mr+Q i) on Although halogens are not a radical in eq. (37), halogens hhave very similar properties of a radical in the temperature which sulfur is existed in a liquid state ‘Thus equilibrium constant K’ in eq. (37) might be repre- sented by the form which contains K,/K term. Hence K’ represented in eg. (12) is reasonable. However, in the equation (10), when a halogen radical attacks S,(ring), the equilibrium constant might be affected by the activity of a halogen radical toward S,(ing). ‘Thus the equilibrium constant K’ can be represented by a ‘equation which contains the activity of a halogen radical such as eq. (12). Therefore, when halogens are added, the reactions are summerized as follows 38) 69)136 Bulletin of Korean Chemical Socioty, Vol. 3. No. 4, 1982 Man Chai Chang and Mu Shik Jhon 4 ed. 5% 18% Ce o 20} 40) ar? -“ ag te oor BT ol «x3 . as = [ae 3 [8% 3 aol Bad ~a-* s = aoe S ger Bremer eT TO g ° = eS Zool § 40) 3 A > 4% Clg 10% @ 20] 40 E are 75 2 : 430 450° 470 490 510 530 Pa 430450470 490510630 Temp. (°K) Figure 1. Viscosity of liquid sulfur containing hslohens as a function of temperature (Sulur-iodine mixtures): dashed experimental data, from rel. 4 line, theoretical curve; 0, 80; oan 49] ceeere ol seg? 7 5 [¥en i“ 2 ol errs ao _- 430 450 470 490 510 Temp. (°K) Figure 2. Viscosity of liquid sulfur containing halogens as 2 function of temprature (sulfur-bromine mixtures); dashed line, theoretical uve; 0, experimental data, fom ret. 4 KM Kg « 00+ KD K By introducing eqs. (39) and (40) into (38) we obtain the following equation 3s KiQet KyMi—1 pay _1—KaMa(1— A) —24. PR RSE a nA ay ‘Tomp.(*K) Figure 3. Viscosity of liquid sulfur containing halogens as @ function of temperature (sulfur-chlorine mixtutes): dashed line, theoretical curve: ©, experimental data, ftom rel. 1. 70) 9 S é B oof fi = ' E ' £ 480 ' 2 ¢ © soo} iso} 2 v =-o- 9-0 4009 “805 60T 700 Temp (*K) Figuer 4, Vopor pressure of liquid sulfur as a function of temperature; dashed line, theoretical cure: 0, experimental data, from ref. 17. 400500600700 Temp. (180 Figure 5. Liquid volume of liquid suttur as a function of temperatura; dashed line, theoretical curve: 0, experimental from sof. 17Viscosity and Thernodynamie Properties of Liquid Sulfur To obtain the P in eg. (41), we introduce the simple valves into A by using experimental values such that 0.1 for Ip, 10 for Bro, and 23 for Cl,, where A is taken as unity fora sulfur radical. Thus, above values are taken as relative values. ‘And the calculated values are compared with the selected values! in Figures 1, to 3. ‘The better results may be obtainable by considering the temperaturedependent activity values of halogen radical toward Sy(ring), and more accurate relations of viscosity- cchaintength. 2. Molar Volume and Vapor Pressure For the calculation of the molar volume and the vapor pressure, the relationship between the Helmholtz free energy, A, and molar volume, V, is used. Ifa common tangent to the points corresponding to liquid land vapor phases is drawn, the vapor pressure is given by the slope of the common tangent, and the abscissas of two points indicate the molar volume of liquid and vapor, res- pectively. To find out the common tangent at a given temeprature, the iterative Newton method is used. Calculated results are presented in Figures 4 and 5, with the experimental values..” The agreement is satisfactory, 3. Entropy and Heat Capacity The entropy is calculated by a the equation ATInfy)y ‘The calculated values are shown in Figure 6 and compared with the selected values.1® Heat capacity at constant volume, C,, and those at cons- tant pressure, Cy, are also calculated by using the following thermodynamic relations, om Sar SH"). ) @ Cy=C,+ TVa2/p a) ‘The calculated results are represented in Figure 7 and the resuls are compared with the experimental values! The agreement between the calculated and experimental values sce satisfactory except inthe 2-ransiton region, Ths dev tion is natural result due to the Brags-Wiliams approxi- rnation. The better resus may be oblainable considering the other improved treatment of order-disorder transition such as Kirkwood method® or Frankel method. 4. Thermal Expansion Coeficint and. Compressibilty The increas of liquid volume is mainly originated from the introduction of fluidized vacancies in the significant structure theory. Thus, the solid-lke volume, V, has boen considered a a constant in the most of the publications of this theory. In the case of liquid sulfur, the sold-tke volume influences severly on the liquid volume itself and related properties, and its change can not be ignored. The contribution to the compressibility andthe thermal expansion coefficient by chan- ‘© of the slid-ike volume is added tothe values contributed by Muidized vacancies inthe following way?! Vs a, ata, “4 Bulletin of Korean Chemical Society, Vol 2, No. 4, 1982 137 vd g ° Sod ; z : 200 = Bod ee tes sig e070 Temp Figure 6. Entiopy of liquid sufu os 2 function of temperature: dashed line, theoretical cure: 0, experimental data, from ret. 18. y Goal) SF os} 2.05] aa0 500600700 Temp. (%) Figure 7. Hest capacity at constant volume of liquid sulfur 8 3 function of temperature; dashed line, theoretical curve: ©, experimental data, fom ref, 11, 19, B=Byt as) Where ay and f have been commonly calculated from the partition function aver)/(Grh), 49 -uver( 206) an ‘The solid-like volume V, has been expressed as a function of temperature and pressure, thus a, and , are 1_(av,)( 9K GAGH, av, )( aK) GEG, © “Thermal expansion cocficient of liquid sulfur exhibits a quite abrupt phenomena at the transition temperature range. By Sifting) conversion to S,(chain), the sold-tike volume is reduced and then by increasing temperatures, the solid-tike volumes increase with forming the long-chained sulfur poly- ‘mer. Thus at the transition temperature, thermal expansion ‘coefficients ae first reduced and then increase with increas-138 Bulletin of Korean Chemicel Society. Val.2. No. 4, 1982 LE 1: Parametric and Experimental Values Used inthe als 2p =140.43(0m%) py =300104cal) ), AH; =57004ea) 65(calfK) for $1); 2186), 2152), 188, 191, 218, 2024, 2048), 434, 435, 470, 24475), 465, 471 vilemt, for Sih; 146, 155, 180, 193, 239, 274, 285, 360, 396, 402, 476, 482, 515, 518 vem, for 84); 2208, 21180), 266, 312, 390, 21481), 476, 2162) for $2); 118 (em, late vibration); 29, 63, 68, 44, 53, Toaetkgm®, for 54); 3.80510", Toye (kgmt, for S;); 2.413%10-% Tiactke, for 82 1.024% 107%, Te0ker, for $2); 1.128% 10-# J. Berkowitz and J. R. Marguart, Chem. Phys, 39, 2151963);4A, ‘Anderson and Y.T. Lob, Can. J. Chem, 47,879 1969):*M. Gardner land A. Rogstad, J.C. Dalion, 1973, $99: 4L. A. Nimon, VD. [Neff, R.E. Cantey, and R.O, Ruttar, J. Mol. Spec. 2,105 (1967): vilem Man Chai Chang and Mu Shik Jhon Temp (4) Figure 8. Thermsl expansion cootficiont of liquid sulfur as 8 function of temperature: dashed line, theoretical curve, 0, experimental data, from ref. 11. ARK. Yee, RIF Batrossand A. Rogstad, JCS. Forafey 68, ° 1808 (1972)-76. 1. Gute, IW. Set, and G. Waddington, gf ’ Amer. Chem. Soc., 16, 1488 (1954); #3. Kao and N.L, Allinger, 2 40) rid Inorg. Chem., 16,35 (1977); J. Donohue, A, Caron and E. Goldish, a ° a J Amer, Chem. So., 83,3748 (961) st oe ‘TABLE 2: Temperatore Dependent Values “TCR Kear Ky Vitem®) core 2 eee Temp.(°K) 20 26 02s)ORIT——MaL.25 480 122 0297 = osos n.d Figure 8, tzothermal compressibility of liquid sulfur at @ 0 8 08mm) a0se function of temperature: dashed line, theortical cuwe: 0, 50 98 0S6S sn 98 exoetimental det, fom ref 1 42x oma 03s 41.02 650 99x10) oss 0301 as 4 from ref, 113 # ftom ref, 12; # from ref. 17 ing temperatures, ‘The calculated results are presented in Figurs 8-9, with the experimental value.!? '5. Parametric Values In the significant structure theory of liquids, there are five typical parameters; E,, Vi.9, a and n, Tn this work, six of @ and_E, have boen substituted for the spectroscopic and experimental data, and the others have been determined by using Seoul Technique.*® ‘The parametric values and experimental values used in the calculations are tabulated in Table I. ‘And temperature depending values are also shown in Table 2. Conclusions. We assumed that in sulfur-halogen system, halogens, 5, (ting), and S,(chain) are in equilibrium each other. Then we obtain the viscosity of liquid sulfur containing halogens by 68 8 @o°0 8 8 ee oO 60086 Figure 10, Arrangement of N spin-lattice sites: @ and @ indicate the up and down directions of spine introducing a new equilibrium equation, The calculated values are in good agreement with experimental values. ‘And the thermodynamic properties of liquid sulfur were also obtained by applying the significant structure theory ofViscosity and Thermodynamic Properties of Liquid Sulfur liquids. Ithas been shown that the agreements between theo ries and experiments are satisfactory. is considered that liquid sulfur is consisted of molecules and the fluidized vacancies of molecular size. The fraction V,/¥V of the degree of freedom is solid-like, and the remain- ing fraction (V—V,)/V can be thought of being gas-like. ‘The solid-like partition function of liquid sulfur is obtain- ed as the product of solid-lke partition function for Sy(ring) and one for Sy(chain), and the gas-like partition function is “obtained as the product of partition function for each com ponents in gaseous states. The Z-transition of liquid sulfur is treated as a kind of ‘order-disorder phenomena using the Bragg-Williams ap- proximation. Appendix 1. AH,—TAS RT 8,2 86 Kemleene(— MTHS) 4a) $5 Kyodo ~ ) ay ses, Keninaen(- In above reactions, the enthalpy changes are taken from re- ference 12 and the entropy changes are obtained from re- ference 12 by using a graphical method. Here set arhistae! aay and from Egs. (A-1) to (A-4), set Kotyt Ketel Kety=1 As ‘And the mole fraction of each component can be obtained as follows wo TF Ket Ket Kite, Te=Kete, 2>Kite (AT) Appendix 2. Sublimation energy E,, can be obtained by using Hess Law depicted as follows E, Salring, sotidy En $,(ring, gas) Ey SSulring, gas) Es ‘Thus sublimation energy B,, can be represented by E,, =E,etEhy therefore E,, and E,, can obtained by the same method, Acknowledgment. This work was supported in part by Bulletin of Korean Chemical Society, Vol. 3. No. 4. 1962 139 Korea Research Center for Theoretical Physics and Che- istry. References (1) R. Fanel, Int Eng. Chem, 38, No. 1, 39 (1946). (2) A.V. Tobolshy, J. Polymer Sei, 25, 220 (1967). (3) A.V. Tobolshy, J. Polymer Sci. 31, 126 (1958). (4) A.V. Tobolsky and A. Eisenberg. J. Amer. Chem. Soc. 81, 780 (1953), (6) T. K. Wiewioroski and F. J. Tour, J. Phys. Chem. 70, 234 (1966). (8) H. Patol and L. 8. Borst. J. Chem. Phys, 88, 822 (1971) (7) F. J. Touro and T, K. Wiewiorowski, J. Phys. Chem, 70, 299 (1966), (8) H. Eyring and M. S. Jhon, “Significant Liquid Structures". John Wiley and Sons Ine.. New York, 1968, (8) M. S. Jhon and H. Eyring, in "Physical Chomistry-An ‘Advanced Treatise, Vol. X Liquid State." Ed. p. 995-376, bby H. Eyring, D. Henderson, and W. Jost, Academic Press, Now York, 1971 (10) M.S. Jhon and H. Eysing. in “Theoretical Chemisty” ‘Advances and Perspectives.” Vol. Il, p. 85-140, Academic Press, Now York, 1978, (11) B. Meyer, “Elemental Sulfur Chemistry and Physics.” John Wiley and Sons Inc.. Now York, 1965, (12) J. Berkowitz and J. R, Marquart. J. Chem. Phys. 38. 275 (1963). (13) W.L. Bragg and Williams, ros. Roy. Soc. A145, 699 (1934) (14) H. Sato, in “Physical Chomistry-An Advanced Treatise, Vol. X Solid State.” by H, Eyring, D. Henderson, and W. Jost, Aeademio Press, New York, 1971, Ed, p. 678-718, (18) H. Eyring, D. Henderson, 8. J. Stover and & M, Eyring. ‘Starstcal Mechanics and Dynamics.” p. 289-308. John Wiley and Sons Inc., New York, 1964 (16) N. €. Frankel. Prog. Theor, Phys. 43, 1148 (1970). (17) J. WW. Mali, "A Comprehensive Treatise on Inorganic ‘and Thearatical Chemistry”, Vol. X. Longmans, London, 1968, Chapter 2 (18) JANAF Thetmechemics! Tables, The Dow Chemical Co Midland, Michigan, 1968. (19) €, D, West, J. Amar .Chom. Soc. 81, 29 (1959). (20) J. 6. Kirkwoad, J. Chom. Phys. 8. 70 (1938) (21) A. Leu, &, Ma and H. Eyring, Proc, Nat. Acad. Sol. (U.S), 72, 1028 (1978), (22) 8. Chang, H. Paik, M. S. Jhon and Ahn, J: Korean Chem. Soc, 8, 33 (1964). (23) M.S. Jhon, J. Grosh, T. Reo and H. Eving.J. Chem. Phys. 44, 1465 (1966).