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Excess volumes of mixtures of acetone +, chloroform +, carbon tetrachloride +, 1,4-dioxan +, and tetrahydrofuran + 1,1-dichloroethane
M-673(N) J. Chem. Thermodynamics 1977,9, 397-399
Notes Excess volumes of mixtures of acetone $, chloroform +, carbon tetrachforide +, 1,4-dioxan +, and tetrahydrofwran + l,l-dichloroethane M. S. DHILLON
a
Department of Chemistry, Guru Nanak Dev University, Amritsar, Punjab, India (Received il June 1976; in revisedform
20 September 1976)
The excess volumes VE of I,l-dichloroethane -t- aromatic hydrocarbon have been reported earlier by us. (I) We now report the excess volumes of acetone +, chloroform -t , carbon tetrachloride f , 1,4-dioxan f , and tetrahyd.rofuran t 1, I-dichloroethane. Acetone, chloroform, carbon tetrachloride (all A.R. grade), l,Cdioxan, tetrahydrofuran (R.D.H. grade), and l,l-dichloroethane (Reidel) were gurified as follows. Acetone was refluxed with successive small quantities of potassium permanganate until the violet colour persisted. It was then dried over potassium carbonate, filtered, and finally distilled. Chloroform was shaken with water, dried over anhydrous calcium chloride for 24 h, and then distilled. Carbon tetrachloride was shaken with potassium hydroxide solution in 50 mass per cent alcohol, removed from the,potassium hydroxide layer, and then shaken with water and small portions of concentrated sulfuric acid. It was shaken with water, dried over anhydrous calcium chloride, and then distihed. 1,4-Dioxan had nitrogen bubbled through it, and was then treated with potassium hydroxide solution. The aqueous layer was removed, refluxed with sodium metal for 6 h, and then distilled. Tetrahydrofuran was kept over sodium hydroxide pellets for 24 h, then refluxed two or three times for 10 h over sodium metal, and then distilled. I,]-Dichloroethane was purified by the method described earlier.(l) The purities of the samples were checked by measuring their densities, which agreed to within 0.00002 g cJn3 with those in the literature.@* 3, The excess volumes were measured by a dilatometer”’ at 293.15 K as a function of composition in a water-filled thermostat controlled to within 20.01 K. The excess volumes VE at 293.15 K as a function of composition are given in table I. The results were fitted by the method of least squares to the equation : VE/cm3 mol-l = x(1 -x){A+B(2xl)fC(2x1)‘). (1) Values of A, B, and C with their standard deviationsc5’ o(V”) are given in table 2. a Present address: Institut fiir Makromolekular i.Br. 7800, West Germany.
Chemie, Albert Ludwigs Universit%t, Freiburg
398
NOTES TABLE x
volumes of mixtures
1. Excess P/cm3
mol-1
AVE/cm3
mol-1
xCH&OCHa 0.1156 0.2115 0.3118 0.3770 0.4745 0.5119
0.069 0.106 0.148 0.165 0.181 0.183
xCHC!la
+ (1 -
0.042 0.048 0.063 0.073 0.077 0.080
+ (1 -
-0.036 -0.049 -0.070 -0.079 -0.088 -0.087
0.1426 0.2152 0.3283 0.4135 0.4747 0.5642
-0.068 -0.099 -0.144 -0.168 -0.182 -0.183
+ (1 -
TABLE (1 - x)C&HCCHa xCH,COCH, xCHC13 xCCl* xl,4-C4HsOa XC&O
2. Values +
mol-
l
x)ClzHCCHa 0.179 0.167 0.151 0.131 0.126 0.079
0.001 -0.001 0.000 -0.003 0.001 0.001
-0.104 -0.100 -0.107 -0.089 -0.065 -0.059
-0.001 -0.005 0.003 -0.001 -0.014 -0.005
+&HCCHa 0.4950 0.5933 0.6438 0.7718 0.8198 0.8740
0.082 0.087 0.081 0.071 0.060 0.041
+ (1 - x)ClzHCCH3 0.4877 0.5181 0.5736 0.6338 0.7026 0.7814
0.007 0.009 0.008 0.009 0.008 0.004
mol - 1 A P/cm3
x)CI,HCCH3
-0.002 0.001 0.003 0.002 0.000 0.000
xCzH80
P/cm3
0.5237 0.5324 0.5447 0.6464 0.7082 0.7718
x1,4-CzHsOz 0.1543 0.2015 0.3041 0.3476 0.4347 0.4664
of composition
0.5735 0.6717 0.7250 0.7894 0.7899 0.8838
-0.013 -0.001 0.004 0.005 0.005 0.006 XCCl,
0.1752 0.2249 0.3278 0.4029 0.4312 0.4681
K as a function X
-0.002 0.006 0.000 0.000 -0.001 -0.002
-0.063 -0.100 -0.110 -0.114 -0.114 -0.113
0.1843 0.3083 0.3603 0.4480 0.4713 0.4926
at 293.15
-0.000 -0.003 0.001 -0.003 -0.003 0.003
-0.084 -0.080 -0.074 -0.065 -0.056 -0.041
0.001 -0.003 -0.006 -0.006 -0,006 -0.004
-0.180 -0.181 -0.176 -0.159 -0.136 -0.078
0.002 0.004 0.007 -0.003 -0.007 -0.003
+ (1 - x)ClzHCCHa
-0.012 -0.016 0.013 -0.001 0.000 0.000
of the parameters
0.5518 0.5560 0.5869 0.6571 0.7174 0.8554
for equation
(1) and standard
A
B
c
0.7242 -0.4283 0.3298 -0.3324 -0.7320
0.0084 0.1151 0.0891 -0.0055 0.0003
-0.0148 0.0008 0.0090 0.2341 0.1503
deviations o( P)/cm3 0.002 0.006 0.002 0.007 0.008
mol-
1
NOTES
399
The excess volumes VE of acetone + 1,1-dichloroethane and carbon tetrachloride + l,l-dichloroethane are positive with maximum values 0.183 cm3 mole1 and 0.087 cm3 mol-l respectively. The excess volumes of chloroform + 1,l -dichloroethane, 1,4-dioxan + 1, I-dichloroethane, and tetrahydrofuran + 1, I-dichloroethane are negative with minimum values -0.113 cm3 mol- ‘, -0.087 cm3 mol- ‘, and -0.183 cm3 mol-’ respectively, indicating the presence of unlike A-B interactions. REFERENCES 1. Dhillon, M. S. J. Chem. Thermodynamics 1974,6, 915. New York. 1950. 2. Timmermans, J. Physico-Chemical Constants of Pare Organic Liquids. Elsevier Pub. Co. Inc. : New York. 1950. 3. Weast, R. C. Handbook of Chemistry and Physics. The Chemical Rubber Co. : Ohio. 1972. 4. Dhillon, M. S. J. Chem. Thermodynamics 1974,6, 1107. 5. Williamson, A. G.; Scott, R. L. J. Phys. Chem. 1960,64,440.
Notes Excess volumes of mixtures of acetone $, chloroform +, carbon tetrachforide +, 1,4-dioxan +, and tetrahydrofwran + l,l-dichloroethane M. S. DHILLON
a
Department of Chemistry, Guru Nanak Dev University, Amritsar, Punjab, India (Received il June 1976; in revisedform
20 September 1976)
The excess volumes VE of I,l-dichloroethane -t- aromatic hydrocarbon have been reported earlier by us. (I) We now report the excess volumes of acetone +, chloroform -t , carbon tetrachloride f , 1,4-dioxan f , and tetrahyd.rofuran t 1, I-dichloroethane. Acetone, chloroform, carbon tetrachloride (all A.R. grade), l,Cdioxan, tetrahydrofuran (R.D.H. grade), and l,l-dichloroethane (Reidel) were gurified as follows. Acetone was refluxed with successive small quantities of potassium permanganate until the violet colour persisted. It was then dried over potassium carbonate, filtered, and finally distilled. Chloroform was shaken with water, dried over anhydrous calcium chloride for 24 h, and then distilled. Carbon tetrachloride was shaken with potassium hydroxide solution in 50 mass per cent alcohol, removed from the,potassium hydroxide layer, and then shaken with water and small portions of concentrated sulfuric acid. It was shaken with water, dried over anhydrous calcium chloride, and then distihed. 1,4-Dioxan had nitrogen bubbled through it, and was then treated with potassium hydroxide solution. The aqueous layer was removed, refluxed with sodium metal for 6 h, and then distilled. Tetrahydrofuran was kept over sodium hydroxide pellets for 24 h, then refluxed two or three times for 10 h over sodium metal, and then distilled. I,]-Dichloroethane was purified by the method described earlier.(l) The purities of the samples were checked by measuring their densities, which agreed to within 0.00002 g cJn3 with those in the literature.@* 3, The excess volumes were measured by a dilatometer”’ at 293.15 K as a function of composition in a water-filled thermostat controlled to within 20.01 K. The excess volumes VE at 293.15 K as a function of composition are given in table I. The results were fitted by the method of least squares to the equation : VE/cm3 mol-l = x(1 -x){A+B(2xl)fC(2x1)‘). (1) Values of A, B, and C with their standard deviationsc5’ o(V”) are given in table 2. a Present address: Institut fiir Makromolekular i.Br. 7800, West Germany.
Chemie, Albert Ludwigs Universit%t, Freiburg
398
NOTES TABLE x
volumes of mixtures
1. Excess P/cm3
mol-1
AVE/cm3
mol-1
xCH&OCHa 0.1156 0.2115 0.3118 0.3770 0.4745 0.5119
0.069 0.106 0.148 0.165 0.181 0.183
xCHC!la
+ (1 -
0.042 0.048 0.063 0.073 0.077 0.080
+ (1 -
-0.036 -0.049 -0.070 -0.079 -0.088 -0.087
0.1426 0.2152 0.3283 0.4135 0.4747 0.5642
-0.068 -0.099 -0.144 -0.168 -0.182 -0.183
+ (1 -
TABLE (1 - x)C&HCCHa xCH,COCH, xCHC13 xCCl* xl,4-C4HsOa XC&O
2. Values +
mol-
l
x)ClzHCCHa 0.179 0.167 0.151 0.131 0.126 0.079
0.001 -0.001 0.000 -0.003 0.001 0.001
-0.104 -0.100 -0.107 -0.089 -0.065 -0.059
-0.001 -0.005 0.003 -0.001 -0.014 -0.005
+&HCCHa 0.4950 0.5933 0.6438 0.7718 0.8198 0.8740
0.082 0.087 0.081 0.071 0.060 0.041
+ (1 - x)ClzHCCH3 0.4877 0.5181 0.5736 0.6338 0.7026 0.7814
0.007 0.009 0.008 0.009 0.008 0.004
mol - 1 A P/cm3
x)CI,HCCH3
-0.002 0.001 0.003 0.002 0.000 0.000
xCzH80
P/cm3
0.5237 0.5324 0.5447 0.6464 0.7082 0.7718
x1,4-CzHsOz 0.1543 0.2015 0.3041 0.3476 0.4347 0.4664
of composition
0.5735 0.6717 0.7250 0.7894 0.7899 0.8838
-0.013 -0.001 0.004 0.005 0.005 0.006 XCCl,
0.1752 0.2249 0.3278 0.4029 0.4312 0.4681
K as a function X
-0.002 0.006 0.000 0.000 -0.001 -0.002
-0.063 -0.100 -0.110 -0.114 -0.114 -0.113
0.1843 0.3083 0.3603 0.4480 0.4713 0.4926
at 293.15
-0.000 -0.003 0.001 -0.003 -0.003 0.003
-0.084 -0.080 -0.074 -0.065 -0.056 -0.041
0.001 -0.003 -0.006 -0.006 -0,006 -0.004
-0.180 -0.181 -0.176 -0.159 -0.136 -0.078
0.002 0.004 0.007 -0.003 -0.007 -0.003
+ (1 - x)ClzHCCHa
-0.012 -0.016 0.013 -0.001 0.000 0.000
of the parameters
0.5518 0.5560 0.5869 0.6571 0.7174 0.8554
for equation
(1) and standard
A
B
c
0.7242 -0.4283 0.3298 -0.3324 -0.7320
0.0084 0.1151 0.0891 -0.0055 0.0003
-0.0148 0.0008 0.0090 0.2341 0.1503
deviations o( P)/cm3 0.002 0.006 0.002 0.007 0.008
mol-
1
NOTES
399
The excess volumes VE of acetone + 1,1-dichloroethane and carbon tetrachloride + l,l-dichloroethane are positive with maximum values 0.183 cm3 mole1 and 0.087 cm3 mol-l respectively. The excess volumes of chloroform + 1,l -dichloroethane, 1,4-dioxan + 1, I-dichloroethane, and tetrahydrofuran + 1, I-dichloroethane are negative with minimum values -0.113 cm3 mol- ‘, -0.087 cm3 mol- ‘, and -0.183 cm3 mol-’ respectively, indicating the presence of unlike A-B interactions. REFERENCES 1. Dhillon, M. S. J. Chem. Thermodynamics 1974,6, 915. New York. 1950. 2. Timmermans, J. Physico-Chemical Constants of Pare Organic Liquids. Elsevier Pub. Co. Inc. : New York. 1950. 3. Weast, R. C. Handbook of Chemistry and Physics. The Chemical Rubber Co. : Ohio. 1972. 4. Dhillon, M. S. J. Chem. Thermodynamics 1974,6, 1107. 5. Williamson, A. G.; Scott, R. L. J. Phys. Chem. 1960,64,440.