journal of MOLECULAR LIQUIDS

ELSEVIER Jonrual of Molecular Liquids, 62 (1994) 199-208

Viscosimetric study of binary mixtures of 1,3-dichloropropane with isomeric butanols

Carlos Lafuente, Htetor Artigas, M.C. L6pez , Ftlix M. Royo and Jos~ S. Urieta

Departamento de Quimica Org~_ica-Quimica Ffsica, Facultad de Ciencias, Universidad de Zaragoza. Ciudad Universitaria, Zaragoza 50009 (Spain)

(Received 15 February 1994; accepted 11 July 1994)

Abstract

From density and viscosity measurements of binary mixtures of 1,3- dichloropropane with isomeric butanols over the whole composition range at 298.15 and 313.15 K and atmospheric pressure, excess viscosities -qE and excess free energies of activation of flow G *E have been calculated. The results are correlated by means of a Redlich-Kister type equation. Both 11E and G *E are negative for all the mixtures.

INTRODUCTION

As an extension of a research program in thermodynamic properties involving hydrocarbon or haloalkane + isomeric butanols mixtures [1-8] we have begun a viscosimetric study of the same kind of mixtures. In this paper we report densities, p, viscosities, 11, excess viscosities, 11 E, and excess free energies of activation of flow, G *E, at 298.15 and 313.15 K and atmospheric pressure of binary mixtures of 1,3-dichloropropane with isomeric butanols. The excess volumes of these mixtures can be found in an earlier paper [4]. No literature lie data are available for these mixtures.

EXPERIMENTAL

1-Butanol (better than 99.8 mol %), 2-methyl-l-propanol and 2-methyl- 2-propanol (better than 99.5 mol %) and 2-butanol and 1,3- dichloropropane (better than 99 mol %) were provided by Aldrich. All

0167-7322/94/$07.00 © 1994 - Elsevier Science B.V. All rights reserved. S S D I 0167-7322 (94) 00776-4

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TABLE 1. Densities, p, and viscosities, 11, of pure components at 298.15 K and comparison with the values reported in the literature [10].

P 11 kg m -a m Pa s

component this paper lit. this paper lit.

1,3-dichloropropane 1180.25 1180.0 * 0.9443 --- 1-butanol 805.85 805.75 2.5562 2.5710 2-butanol 802.40 802.41 3.0596 2.998 2-methyl- 1-propanol 797.98 797.8 3.3603 3.330 2-methyl-2-propanol 781.00 781.2 4.4126 4.438

* Reference 11.

isomeric butanols were dried over activated molecular sieves type 0.3 nm from Merck. The purity of the chemicals was checked by GLC and no further purification was considered necessary.

The densities of the pure components and mixtures were measured by means of an Anton-Paar DMA-58 vibrating tube densimeter. Calibration was carried out with deionized doubly-distilled water and dry air. The uncertainty of density measurements was + 1 x 10 -2 kg m -3.

Viscosities were determined using an Ubbelhode viscosimeter with a Schott-Ger~ite automatic measuring uni t model AVS-440. The viscosimeter were calibrated also with deionized doubly-distilled water. Kinetic energy corrections were applied to the experimental data. The estimated error was + 1 × 10 -4 m Pa s. Details of the procedure have been previously described [9].

Table 1 shows the experimental values of density and viscosity for the pure components at 298.15 K, compared with the published values [10,11].

RESULTS AND DISCUSSION

The excess viscosities and excess free energies of activation of flow were calculated using the following equations:

11 E-" 11 " (X1 111 + X2 "q2) ( 1 )

G ' E = RT [ In riV - (Xl In rllV1 + x21n r12V2) ] (2)

were rl, rl~ ands2 are the absolute viscosities (Pa s) of the mixture and of

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the pure components, V, V1 and V2 are the molar volumes (m3 mol-1) of the mixture and of the pure components, and xi is the mole fraction of component i in the mixture.

The densities and viscosities together with the excess functions are gathered in table 2.

The values of "tl E and G *E were fitted at each temperature to a Redlich- Kister type equation by the method of least squares:

y E = Xl (l_Xl) ~ ai (2Xl_l)i (3)

where al, a2, etc. are adjustable parameters and xl is the mole fraction of 1,3- dichloropropane. The values of the parameters together with the standard deviations o(Y E) are given in table 3.

E . yeEx 2/(n-p) ]m o(Y E) = [ E (Yealc p) (4)

where n is the number of experimental data and p is the number of parameters.

TABLE 2. Densities, p, viscosities, 1], excess viscosites, 1]E, and excess free energies of activation of flow, G *E, of binary mixtures 1,3- dichloropropane(1) + isomeric butanols(2) at the indicated temperature.

D 1] 1~ E G *E Xl kg m-a m Pa s m Pa s J mol-1

1,3-dichloropropane(1) + 1-butanol(2) at 298.15 K 0.0958 843.02 2.1387 -0.2630 -205.2 0.2016 883.41 1.7730 -0.4582 -407.9 0.3004 920.68 1.5118 -0.5602 -557.8 0.3983 957.40 1.3203 -0.5939 -651.0 0.5002 995.36 1.1765 -0.5734 -684.5 0.5993 1032.16 1.0714 -0.5188 -671.7 0.6997 1069.17 0.9963 -0.4321 -604.0 0.7997 1106.00 0.9461 -0.3211 -485.9 0.9000 1143.00 0.9256 -0.1799 -293.8

1,3-dichloropropane(1) + 2-butanol(2) at 298.15 K 0.1002 840.48 2.2298 -0.6178 -489.1 0.2005 878.17 1.6834 -0.9520 -890.3 0.3002 915.55 1.3459 -1.0787 -1152.1 0.4005 953.11 1.1342 -1.0782 -1282.4

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TABLE 2. Continued

p 1" I TIE G*E Xl kg m-a m Pa s m Pa s J mol "l

0.4986 990.01 1.0306 -0.9743 -1233.6 0.6027 1029.09 0.9587 -0.8260 -1109.7 0.6951 1063.72 0.9141 -0.6752 -959.2 0.8051 1105.18 0.8940 -0.4626 -695.6 0.9113 1145.58 0.8997 -0.2322 -373.4

1,3-diehloropropane(1) + 2-methyl- 1-propanol(2) at 298.15 K 0.0989 836.98 2.5227 -0.5987 -399.9 0.2041 877.82 1.9479 -0.9193 -709.1 0.3021 915.54 1.6040 -1.0264 -881.3 0.3988 952.53 1.3726 -1.0242 -962.5 0.5019 991.79 1.1941 -0.9536 -982.8 0.6020 1029.68 1.0781 -0.8278 -920.8 0.7040 1068.04 1.0006 -0.6588 -784.1 0.8027 1105.19 0.9476 -0.4734 -608.8 0.8982 1141.22 0.9412 -0.2491 -326.0

1,3-dichloropropane(1) + 2-methyl-2-propanol(2) at 298.15 K 0.1010 819.69 2.7787 - 1.2836 -754.5 0.2021 858.90 1.8767 -1.8350 -1337.3 0.3082 900.52 1.3931 -1.9506 -1668.3 0.4082 940.06 1.1798 - 1.8171 - 1697.4 0.5066 979.24 1.0615 -1.5941 -1583.3 0.6080 1019.72 0.9826 -1.3213 -1387.8 0.7071 1059.51 0.9381 -1.0221 -1125.2 0.8080 1100.33 0,9128 -0.6974 -809.3 0.9003 1138.27 0.9114 -0.3787 -463.5

1,3-dichloropropane(1 ) + 1 -butanol(2) at 313.15 K 0.0958 830.32 1.4879 -0.1735 0.2016 869.51 1.2608 -0.2971 0.3004 905.91 1.1007 -0.3605 0.3983 941.63 0.9831 -0.3823 0.5002 978.67 0.8935 -0.3721 0.5993 1014.43 0.8317 -0.3369 0.6997 1050.79 0.7876 -0,2828 0.7997 1086.94 0.7600 -0.2125 0.9000 1123.44 0.7528 -0.1215

-224.4 -428.9 -571.4 -656.4 -687.9 -663.6 -593.2 -474.9 -289.1

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TABLE 2. Continued

p 1] 1~ E G *E xl kg m-a m Pa s m Pa s J mol "1

1,3-dichloropropane(1) + 2-butanol(2) at 313.15 K 0.1002 826.45 1.3686 -0.3157 -469.8 0.2005 863.23 1.1032 -0.4799 -809.7 0.3002 899.72 0.9402 -0.5423 -1006.8 0.4005 936.49 0.8403 -0.5410 -1080.1 0.4986 972.51 0.7841 -0.4982 -1046.8 0.6027 1010.83 0.7468 -0.4305 -948.5 0.6951 1044.90 0.7254 -0.3587 -825.1 0.8051 1085.77 0.7214 -0.2517 -603.6 0.9113 1125.74 0.7371 -0.1288 -321.5

1,3-dichloropropane(1 ) + 2-methyl- 1-propanol(2) at 313.15 K 0.0989 823.50 1.6371 -0.3252 -382.4 0.2041 863.16 1.3267 -0.4972 -656.4 0.3021 899.84 1.1266 -0.5683 -827.5 0.3988 935.96 1.0005 -0.5671 -885.8 0.5019 974.30 0.8964 -0.5356 -905.2 0.6020 1011.35 0.8306 -0.4696 -844.6 0.7040 1049.19 0.7890 -0.3770 -715.6 0.8027 1085.72 0.7599 -0.2762 -559.4 0.8982 1121.43 0.7565 -0.1539 -326.5

1,3-dichloropropane(1) + 2-methyl-2-propanol(2) at 313.15 K 0.1010 802.77 1.5076 -0.4484 -581.7 0.2021 841.55 1.1639 -0.6595 -991.2 0.3082 882.68 0.9559 -0.7282 -1228.0 0.4082 921.71 0.8566 -0.6963 -1254.9 0.5066 960.31 0.7978 -0.6260 -1186.3 0.6080 1000.37 0.7579 -0.5329 -1059.4 0.7071 1039.75 0.7469 -0.4139 -843.4 0.8080 1080.45 0.7328 -0.2956 -635.7 0.9003 1118.22 0.7431 -0.1642 -365.2

204

0 ~

0 ° ~

Sedm/Bl~

J f I _ ~

O ~

o ~.~ d

.~ •

¢?, ~, "~ '7, s ~dtU/~k

~c6

205

o i l I ~-~'-~--~--~= ~ / = ~--- I ° °- ~o

• .,.~ ~

~ O

!_lOre f I ~,D ~

206

TABLE 3. Coefficients, a~, of equation (3) and standard deviations, ts(YE), determined by the method of least squares.

Function ao al a2 a3 t~(Y E)

1,3-dichloropropane(1) + 1-butanol(2) at 298.15 K tie (m Pa s) -2.3018 0.7986 -0.3450 -0.2477 0.0013 G*E(J mol d) -2746.9 -189.5 -110.2 -590.3 1.9

1,3-dichloropropane(1) + 2-butanol(2) at 298.15 K ~E (m Pa s) -3.9090 2.4958 - 1.5043 -0.0240 0..0043 G*E(J mol d) -4969.4 1541.6 -117.1 -1577.9 12.0

1,3-dichloropropane(1) + 11E (m Pa s) -3.8098 G*E (J mol-1) -3929.7

2-methyl-l-propanol(2) at 298.15 K 2.0017 -1.4263 0.7549 0.0029

455.9 -290.4 148.3 8.8

1,3-dichloropropane(1) + rl E (m Pa s) -6.4467 G*E(J mol-0 -6460.1

2-methyl-2-propanol(2) at 298.15 K 5.1034 -4.2780 1.7707 0.0034 3297.9 -721.8 -2055.9 20.0

1,3-dichloropropane(1 ) + 1-butanol(2) at 313.15 K 11E (m Pa s) - 1.4865 0.4808 -0.2846 -0.1223 0.0005 G*E(J mol d) -2742.0 -56.3 -238.8 -545.5 2.6

1,3-dichloropropane(1) + 2-butanol(2) at 313.15 K tiE (m Pa s) -1.9932 1.1061 -0.8644 0.1371 0.0011 G*E(J mol d) -4210.1 1289.2 -648.5 -792.7 6.1

1,3-dichloropropane(1 ) + 2-methyl- 1-propanol(2) at 313.15 K tie (m Pa s) -2.1342 1.0297 -0.7945 0.2883 0.0034 G*E(J mol-1) -3601.5 556.4 -511.3 -205.1 7.8

1,3-dichloropropane(1) + 11E (m Pa s) -2.5292 G*E (J mold) -4811.0

2-methyl-2-propanol(2) at 313.15 K 1.7176 -1.3334 0.3528 0.0035 2190.1 -779.8 -1165.7 13.0

The curves in figures 1 and 2 show the excess functions, "liE and G *E, for the four systems at both temperatures (298.15 and 313.15 K). They are negative over the whole composition range. At 298.15 K tIE and G *E increase in absolute value in the sequence: 1-butanol < 2-methyl-l-propanol < 2-butanol < 2-methyl-2-propanol, at 313.15 K this sequence changes a little because for

207

the mixture containing 2-methyl-l-propanol rl E is more negative than for the mixture with 2-butanol. Minimum Ti E and G*E values are shifted towards lower concentrations of 1,3-dichloropropane. This shift is in the sequence: 1- butanol < 2-methyl-1-propanol < 2-butanol < 2-methyl-2-propanol.

The excess functions decrease in absolute value for all the mixtures when the temperature increases. The decrease, in relative terms, is in the order: 1- butanol < 2-methyl-1-propanol < 2-butanol < 2-methyl-2-propanol.

Negative I] E and G*E values correspond, according to Fort and Moore [12], to systems in which at least one of the components exhibits association, and in which solute-solvent complexes have low stability. Butanols are self- associated compounds by hydrogen bonds. In the 1,3-dichloropropane there is no association but there are dipole-dipole interactions. Therefore, in the mixture there is a breaking of the self-association in the butanols and of the dipole-dipole interaction in the 1,3-dichloropropane [4], these two effects have a negative influence on the excess viscosity. There must also be a specific interaction between the Cl-group in the dichloroalkane and the OH- group in the butanol which has a positive influence on the excess viscosity, but this interaction is not as marked as the two previous effects as can be seen from the high negative values of G *E.

Similar viscosimetrie behaviour has been previously observed by other authors [13] for mixtures of a chloroalkane + butanols.

Acknowledgements

The authors are grateful for financial assistance from Direcci6n General de Investigaci6n Cientifica y Ttcnica (DGICYT), Project N ° PS90-0115

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