M-2182

J. Chem. Thermodynamics1!%?3,20,581-587

Activity coefficients of the tetramethyl compounds of Group elements in n-alkane solutions from g.1.c. measurements
T. M. LETCHER, J. D. SEWRY R. C. BAXTER, A. BEAN, and

14

Departmentof Chemistry,Rhodes University, Grahamstown, 6140,South Africa (Received23 June 1987;infinal form 5 October 1987)
The activity coefficients at infinite dilution at various temperatures have been determined by g.1.c. for all the tetramethyl compounds of Group 14 elements in the solvents n-dodecane, n-hexadecane, n-eicosane, and n-tetracosane; the excess partial molar enthalpies at infinite dilution have been calculated. The activity coefficients have been discussed in terms of the quasi-lattice theory. The segment and contact-point treatments previously used for n-alkane mixtures and for (an n-alkane + benzene) have been extended to (an n-alkane + a tetramethyl compound).

1. Introduction
at various temperatures have been determined by g.1.c.) for all the tetramethyl compounds of the Group 14 elements: C, Si, Ge, Sn, and Pb in each of the n-alkane solvents: C12Hz6, C16H34, GOH429 and W-ho. Another purpose of this work was to investigate the applicability of the quasilattice theory@-@ to mixtures of this kind. The central atoms of the tetramethyl compounds are hidden by the relatively large methyl groups and as a result it is possible that activity coefficients, for the mixtures considered here, could be explained in terms of tetramethyl CH,-, terminal n-alkane CH,-, and middle n-alkane -CH2- group interactions.
In this work the activity coefficients at infinite dilution

2. Experimental
The n-alkane solvents C12Hz6, C16H3.+, C&H,,, and Cz4H,, were supplied by Aldrich and used without further purification. The tetramethyl methane was supplied by African Oxygen, the tetramethyl silane by Merck, and the tetramethyl germane, tetramethyl stannane, and tetramethyl plumbane by Alpha Division Chemical Company. They were used without further purification.
0021-9614/88/050581+07 $02.00/O 0 1988 Academic Press Limited

582

T. M. LETCHER

ET AL.

The g.1.c. apparatus used in this work has been described., 7, The columns used were 6.1 mm o.d. stainless-steel tubing and ranged between 1 and 2 m in length. The support used was celite SO/l00 mesh and was supplied by B.D.H. The solvent loading ranged between 5 mass per cent (for C12Hz6) and 16 mass per cent (for C,,H,,). It was necessary to use a catharometer detector because the flameionization detector was not suited to metal compounds. In spite of this the sample injection was kept below 0.5 pmol and the infinitely dilute condition was ensured. Pure dry nitrogen was used as the carrier gas and a calibrated bubble flowmeter was used to measure the flow rate which ranged between 0.2 and 1.5 cm3. s - . The column temperature was controlled to within 0.01 K.

3. Results The activity coefficients yr3 were calculated from the relations (1) to (4) in reference 8.7 The retention volumes were determined from peak averages.(9) In all cases the peaks obtained were symmetrical. No effect on the activity coefficients was obtained with different column loadings or carrier-gas flow rates. Furthermore, no significant retention was obtained using the uncoated support. We concluded from these three results that the effects of non-equilibration and adsorption were negligible. To ensure control over possible solvent loss and to check the column loadings, n-pentane, n-hexane, and cyclohexane, whose retention properties are well documented, were injected before and after each tetramethyl compound and the retention properties determined. Only for the C12Hz6 columns was it necessary to correct for solvent loss. In general these columns were not used for more than 3 h before being discarded. The densities p of the hydrocarbons and of the tetramethyl solutes(10-3 were obtained from the literature. The densities of the tetramethyl compounds were summarized: p/(g.cmd3) = .io &{(T/K)-273.15), (1)

and the coefficients are given in table 1. Similarly, the virial coefficients B,, of the solutes were obtained from the literaturelO. 14-17) and summarized according to the
t In this work. the subscript 1 refers to solute, 2 to carrier gas, and 3 to the solvent.

TABLE Compound WH,), WX3L WCHd, WCH,), PWH,), Reference 10 11 12 11 13

1. Coefficients 43 0.6136 0.6634 0.9947 1.3347 2.034

A, for equation -104A, 11.26 10.42 7.24 16.47 19.4

(1) - lOA, 1.67 109A, - 14.23

3.06

9.46

~{M(CH,),}

(M

= C, Si, Ge, Sn, OR Pb) IN AN n-ALKANE

583

TABLE 2. The coefficients for equation (2) Compound

WH,),

Reference
10

Bo 1142.3 1459.3 1879.3 2219.7 3138.7

-4 11.1 14.1 17.4 24.0 45.9

lOB,

- lOB,

WH,), GeWA WCW4 PWH,),

14 15 16 17

0.90 0.91 1.13 2.22 4.89

3.91 2.83 3.90 10.02 22.82

equation: B,,/(cm3 .mol-l) = .gO B,{(T/K)-273.15).

(2)

The coefficients are given in table 2. The vapour pressures pT of the tetramethyl compounds were also obtained from the literature(O* 15, 18-2o) and the results fitted to the Antoine equation: lg(p,/kPa) = A - B/(C + T/K),

(3)

using a non-linear regression technique. The results are given in table 3. The mixed virial coefficients B,, were calculated from McGlashan and Potters equation ) and Hudson and McCoubreys combining rules:(22, 23)
B,,/I/,, 12 =

0.430-0.886(&,/T)-0.694&,/T)* -O.O375(n,,1)K. 12/n4.5>

(4)
(5)

where

Vc. Tc.
and
12 = 1WT,, 1 =

12

<K!:1+

K!i,2)3/f3, 1 122)12K. + K/cfi232Fi 1 I K, 22/I,

11 T,, 22P2U1 (Ill +~22>Kti,,

(6)

(7)
(8)

n12

6%

+n,)P.

The critical coefficients and ionization energies used in the calculations are given in table 4. The value of n, (referring to the tetramethyl compounds) was taken as 5 and n, (referring to the carrier gas, nitrogen) was taken as 1.
TABLE 3. The coefficients of the Antoine equation for the solutes used in this work Compound
WHA

Reference 10 18 15 19 20

-C

SW-M, Ge(CH,h SWW4 PWHd,

5.8392 5.0744 6.8825 5.9473 6.1384

938.23 1034.73 1523.10 1179.27 1374.69

37.90 37.41 2.71 51.91 50.30

584

T. M. LETCHER

ET AL.

TABLE 4. The critical constants and ionization energies I used in the calculation of the mixed second virial coefficients B, 2 Compound WH,), SW-l,), WCH,), WCH,), PWW, NZ V,/(cms mol - r ) 303.0 362.1 315.2 394.6 398.5 90.1 UK 433.8 447.3 473.1 519.4 569.0 126.1 Reference 10 24 24 24 24 10 I/(MJ . mol- ) 0.993 0.95 0.89 0.83 0.17 1.40 Reference 25 25 25 estimated 25 25

TABLE 5. The experimental activity coefficients y Ts, x obtained from equation (8), and the difference IAy;s/between y?s and y;,(calc) obtained from equations (9) and (10) Solute YF3 x IbT3l Solute
YF3

IW3l

Solute

YY3

IArGI

WH,L,

WCH,),
WH,),

1.143 0.302 1.222 0.311 1.123 0.275 1.181 0.311 1.084 0.372 1.153 0.368 1.062 0.338 1.120 0.335 1.043 0.305 1.080 0.294 1.024 0.426 1.083 0.417 1.000 0.383 1.042 0.372 0.981 0.343 1.001 0.334 0.959 0.454 0.998 0.454 0.939 0.409 0.957 0.387

0.002 0.012 0.004 0.003 0.009 0.006 0.010 0.007 0.011 0.001 0.012 0.003 0.009 0.002 0.008 0.016 o.ooo 0.016 0.001 0.018

WCH3L WCH,), WJH,), PWCH,)., WH3), PWCH,), Si(CH,), PWCW, WW, WCH,),

C,*Ha6 at 273.15 K 1.201 6.297 0.003 1.207 0.307 0.019 CIzHzs at 293.15 K 1.182 0.297 0.005 1.158 0.275 0.008 at 293.15 K 1.145 0.361 0.002 1.132 0.364 0.001

Ge(CH,),

1.198 0.294

0.008

SW%),
WH,),

Ge(CH,),

1.169 0.294

0.002

C,,H,,

Sn(CH,L
WH3L

GeWH,),

1.130 0.356

0.008

WCH,), WHA WCH,L WH,), WCH,), C(W), SnlCH,), CW-U WCH,), CO-U, SnWM, WW, WCH,),

C,6H34 at 313.15 K 1.122 0.333 0.005 1.090 0.325 0.005 C,,Hs, at 333.15 K 1.103 0.308 0.014 1.059 0.294 0.001

WCH,),

1.090 0.322

0.008

WCH,),

1.063 0.298

0.003

C20H42 at 313.15 K WCH,), 1.090 0.419 0.005 PWH,), 1.059 0.413 0.001 C,,H,, WH,), PWCH,), C,,H,, Si(CH3)., WCH,), C,,H,, WCH3)4 WCH,), C,,H,, Si(CH,), PMCH,), at 333.15 K 1.060 0.380 0.005 1.020 0.373 0.001 at 353.15 K 1.033 0.334 0.003 0.973 0.325 0.009 at 333.15 K 1.028 0.454 0.003 0.992 0.456 0.002 at 353.15 K 0.997 0.413 0.005 0.941 0.400 0.007

WCH,),

1.055 0.407

0.008

WCH,),

1.022 0.375

0.001

W-X,),

0.990 0.345

0.010

Ge(CH,),

0.983 0.446

0.008

WCH,),

0.945 0.417

o.ooo

Y~{M(CH~)~} (M = C, Si, Ge, Sn, OR Pb) IN AN n-ALKANE

585

McGlashan and Potters equation was tested by using it to determine the value of B, I for each of the tetramethyl compounds. In all cases, the results were within 3 per cent of the experimentally determined values. The activity coefficients yFS are given in table 5. The estimated error in yFj is estimated to be within + 0.01.

4. Discussion
The Guggenheim-Miller-Flory-Huggins equation:26 I/$+X,
(9)

In ~7~ = ln(l/r)+(l-

has been applied here. As before r is taken as the ratio of the solvent and solute molar volumes (3-6) The molar volumes of the n-alkane solvents were obtained from the literature.() Perhaps the most interesting outcome of this work is that x, for a particular solvent at temperature T, is independent of the central atom of the tetramethyl compound. In view of the relatively large size of the methyl groups to the small central atom, this result is understandable. All the x values from this work can be summarized by one single equation: 2 = -{1.41+0.293(n-12)/4}10-3(T/K)+{0.300+0.097(n-12)/4), (10)

where n is the number of carbon atoms in the n-alkane molecule. Using equations (9) and (lo), yy3(calc) has been determined. The difference between these calculated values and the experimental values are given in table 5. The values of x have been fitted to the contact-point theory previously used by Gainey and Young. (3) As before the (-CH,-) n-alkane middle group, designated a, was assigned 2 points and the (CH,-) n-alkane end group, designated b, was assigned 3 points. The (CH,-) tetramethyl group, designated c, was also assigned 3 points, and the total number of contact points on the tetramethyl molecule was taken as 12. The equation used in this work becomes {(n+1)~/12}+3(n-2)(n+l)-w,b/kT
where Waby wao and wbc are the interchange

= (3w,,/kT)+(n-2)w,,/kT,

(11)

energies for the respective segments. Only the values of x at 313.15 K (extrapolated in some cases) have been analysed. The value of w,,/k = 53.6 K was obtained from the activity coefficients for (n-alkane + n-alkane)3 and our calculated values for w,,/k and w,,/k are 21.67 K and - 5.22 K, respectively. These values together with equations (9) and (11) have been used to calculate yr3(calc) and the results are given in table 6. The segment model (4S has also been extended to include (CH,-) tetramethyl 8, units. Using a similar formalism to that developed before27~28) the relevant equation becomes
- TX/4m, = {2(n -2)mb/(2m, + n-2)2)(W,b/k) - {h&h&+ ?I-2)}(w,,/k) (12) -{(H-2)/(2m,+n-2)}(W,,/k).

In this work we have assumed that the (CH,-) tetramethyl compound unit is identical to the (CH,-) n-alkane end group unit. As a result m, = mb, wab= w,, and

586

T. M. LETCHER

ET AL.

TABLE 6. The difference lAyTac,l between experimental ym at 313.15K and yl(calc). The values of IAy;3(1)1were i3 obtained using equation (10) and IAyrs(2)) using equation (12). In some cases the experimental activity coefficients yK have had to be extrapolated to 313.15 K

lW&l

Solute

IWdlI

IW3Q)I __0.001 0.011 0.002 0.006 0.014 0.003 0.001 0.000

Solute

C,zHzc, V-%h
WCH,h WH,), SCHJ, WH,), WCH,), WH,)., WCW4 0.021 0.030 0.012 0.019 0.006 0.014 0.005 0.009 0.001 0.009 0.002 0.008 0.007 0.001 0.011 0.015 0.024 0.010 W-L 0.013 0.017 CmH,, 0.027 0.016 G&o 0.006 0.006

WCH,),

0.007

0.027

WCH,),

0.028

0.001

PWH,),

0.019

0.006

W&h,

0.020

0.035

W bc = 0. The best-fit values are mb= m, = 5.57 and w,,/k = w,,/k = 15.45 K. These values together with equation (11) have been used to calculate rpj(calc) and the results are given in table 6. Equation (12) fits the results very much better than does equation (11). The results in table 6 show that the average AyT3(2) is 0.008 while the average Ay;,(l) is 0.161. The excess partial molar enthalpies at infinite dilution calculated from y;D3 in

TABLE 7. Excess partial molar enthalpies at infinite dilution at various temperatures. The error is estimated to be +400 J. mol- Solute ___ J.mol-

HY"

H". Oc
Solute 1 J.mol-

HE.LK
Solute 1 J.mol-t

HE. 10
Solute 1 J.molmi

HE.X,
Solute A J.mol-

WH,), C(CH,L, C(CW, C(CHd, WH,), C(CH,),

590 710 830 860 990 1030

WH,), Si(CH,), SCH,), Si(CH,), Si(CH,), Si(CH,),

560 1010 780 1210 1400 1440

C,2H26 at 283.15 K Ge(CH,), 840 Sn(CH,), C,,H,, at 303.15 K Ge(CH,), 1370 Sn(CH,), C16H34 at 323.15 K Ge(CH,), 1210 Sn(CH,), C,,H,2 at Ge(CH,), C,,H,, at Ge(CH,), 323.15 K Sn(CH,), 1260 343.15 K 1460 Sn(CH,),

1110 1010 1580 1640 1920 1990

Pb(CH,), Pb(CH,), Pb(CH,), Pb(CH,), Pb(CH,), Pb(CH,),

1400 1370 1210 2450 2450 2530

C,,H,, at 343.15 K Sn(CH& Ge(CH,), 1780

y{~(cH,),)

(M = C, Si, Ge, Sn, OR Pb) IN AN n-ALKANE

587

table 5 are given in table 7. The HF, m values increase with increasing length of the n-alkane carbon chain and also increase with increasing atomic number of the central atom of the tetramethyl compound. The authors wish to thank the C.S.I.R. (South Africa) for financial assistance.
REFERENCES 1. Letcher, T. M. Chemical Thermodynamics Vol II. McGlashan. M. L.: Editor. Specialist Periodical Reports, The Chemical Society: London. 1978, Chapter 2. 2. McLure, I. A.; Bennett, J. E.; Watson, A. E. P.; Benson, G. C. J. Phys. Chem. 1965, 69, 2759. 3. Gainey, B. W.; Young, C. L. Trans. Faraday Sot. 1968, 64, 349. 4. Letcher, T. M. J. Chem. Thermodynamics 1975, 7.969. 5. Letcher, T. M.; Jerman, P. J. Chem. Thermodynamics 1976, 8, 127. 6. Letcher, T. M.; Jerman, P. J. Chem. Thermodynamics 1979, Il. 945. 7. Letcher, T. M. J. Chromatography 1978, 166, 257. 8. Letcher, T. M.; Marsicano, F. J. Chem. Thermodynamics 1974, 6, 501. 9. Hicks, C. P. Thesis, Bristol. 1970. 10. Selected Values of Properties of Hydrocarbons and related Compounds. American Petroleum Institute, Research Project 44, Thermodynamics Research Centre: Texas A and M University, College Station. 1980. 1 I. Ahmed, A.; Dixon, D. T.; McGlashan, M. L. J. Chem. Thermodynamics 1977,9, 1087. 12. Mogul, P. H.; Hochberg, M. C.; Michiel, R.; Nestel, G. K.; Wamsley, B. L.; Coren, S. D. J. Chem. Eng. Data 1974, 19, 4. 13. Grutlner, G.; Drause, E. Berichte der Deutschen Chemischen Gesellschaft 1916, 49, 1415. 14. Bottomley. G. A.; Naim, D. B. Aust. J. Chem. 1977, 30, 1645. 15. Valerga, A. J.; Kilpatrick, J. E. J. Chem. Phys. 1970, 52, 4545. 16. Brewster, E.; McGlashan, M. L. J. Chem. Thermodynamics 1977, 9, 1095. 17. Abraham, M. H.; Irving, R. J. J. Chem. Thermodynamics 1979, 11, 544. 18. Aston, J. G.; Kennedy, R. M.; Messerly, G. H. J. Am. Chem. Sot. 1941, 53,2343. 19. Bullard, R. H.; Haussmann, A. C. J. Phys. Chem. 1930, 34, 743. 20. Good, W. D.; Scott, D. W.; Lacia, J. C.; McCullough, J. P. J. Phys. Chem. 1959, 63, 1139. 21. McGlashan, M. L.; Potter, D. J. B. Proc. Roy. Sot. A 1%2,267,478. 22. Hudson, G. H.; McCoubrey, J. C. Trans. Faraday Sot. 1960, 56, 761. 23. Cruickshank, A. J. B.; Windsor, M. L.: Young, C. L. Trans. Faraduy Sot. 1966, 62, 2341. 24. Rummens, F. H. A.; Rajan, S. Can. J. Chem. Eng. 1979, 57, 349. 25. Vedeneyev, V. I.; Gurvich, L. V.; Kondratyev, V. N.; Medvedev, D. A.; Frankevich, Y. L. Bond Energies, Ionization Potentials and Electron Ajinities. Arnold: London. 1966. 26. Ashworth, A. J.; Everett, D. H. Trans. Faraday Sot. MO, 56, 1609. 27. Letcher, T. M.; Jerman, P. J. S. Afr. J. Chem. 1978, 31, 139. 28. Cruickshank, A. J. B.; Gainey, B. W.; Hicks, C. P.; Letcher. T. M.; Young, C. L. Trans. Farada) Sot. 1%9, 65, 2357.