Bromley 1970
Bromley 1970
Bromley 1970
A pressure calorimeter has been designed. constructed, and used to measure the
heat capacity of sea salt solutions from 80' to 2OO0C. and up to 12% salinity.
C, valuer calculated from experimental measurements are correlated by the use
of extended Debye-Hirckel theoty. Heat capacity values at saturation, C,.,, and partial
and apparent valuer for sea salts and water are included. The heat capacities,
C,-, and C,, are in general considered accurate to fO.OO1 cal. per gram per "C.
with a maximum error of f0.003.Values are smoothed to include previously measured
heat capacities between 0' and 8 0 ' C . All valuer are in defined calories = 4.1840
absolute iodes per gram per C. Enthalpies are given in calories per gram, referred
to pure water and salts a t infinite dilution as zero at Oo C.
246 Journal of Chemical and Engineering Doto, Vol. 15, No. 2, 1970
4c TO
SYNCHRONOUS
I
7
OIL
MOTOR OIL TO PUMP
FROM OIL HEATER
in an Inconel-w tube, but electrically insulated from it Monel can, supported vertically on a pointed shaft
by compacted magnesium oxide insulation, helically wound and aligned radially by a Teflon sleeve. The master magnet
on gold-plated copper bar supports. Other heaters which was driven by a synchronous motor a t 300 r.p.m. The
proved unsatisfactory included one of anodized aluminum, heat of stirring alone would cause about 0 . l o C . per hour
glass fiber-insulated wire in a copper tube, Teflon-insulated rise if the bomb were perfectly insulated.
wire, and several other variations of these. Bomb temperature measurements were made using a pla-
The energy input to the sample chamber was from a tinum resistance thermometer calibrated by the National
60-cycle, 110-volt constant-voltage source. I t was measured Bureau of Standards. A Leeds & Northrup Mueller bridge,
with a calibrated Sangamo rotating standard, J-5. Its sensitive null detector, and recorder were used to detect
absolute accuracy was &0.17%, although its reproducibility, temperature changes to k0.0002° C.
which is more important, was 10.02%. This easily satisfied Most other temperatures were measured with iron-
the desired accuracy and was simpler to use than the usual constantan thermocouples using a Leeds & Northrup K-5
d.c. system employing accurate measurement of voltage potentiometer. A few temperatures were displayed directly
and amperage as functions of time. on the console by means of indicating thermometers
The stirrer consisted of a slave magnet in a gold-plated accurate to about 1"C.
Journal of Chemical and Engineering Data, Vol. 15, No. 2, 1970 247
PROCEDURE THEORY
The sea water used for all measurements was taken from The procedure used to evaluate the hypothetical zero
the end of the pier a t Scripps Institution of Oceanography, time and the temperature rise a t that time is the same
La Jolla, Calif., about midway between the free surface as that used previously ( 4 ) .
and the sand. I t was filtered and acidified with concentrated The present calorimeter is essentially one of constant
H S 0 4 to pH 4 as previously described ( 4 ) . The amount volume in which evaporation (or condensation) is expected
of concentrated H2S04 required was about 120 p.p.m. to occur as the temperature rises. The procedure used
For concentrations other than that of normal (La Jolla) is essentially that due to Osborne (9) and corrects for
sea water (about 3.34%), water was carefully removed by the heat of vaporization and the expansion of liquid water.
evaporation, or distilled water was added. The heat, aQ, required to raise the calorimeter and its
All samples were analyzed for chloride by titration with contents an amount dT is given by
silver nitrate, using the Knudsen (11) method. The normal
8Q = dH - VdP (1)
distribution of ions (12) was assumed. The sea salt content
was finally expressed as per cent salinity-i.e., parts per If this is applied separately to the calorimeter and its
hundred as opposed to parts per thousand, O/OO, as used contents and the results are added, one obtains
in oceanography. This is approximately the percentage of
total dissolved solids (1%salinity = 1.00465 total dissolved ( V - Mu)( h ' - h )
solids). 6Q = KdT + MC,,dT -t d
(u' - u )
- ( V - M u ) d P (2)
After weighing, filling, and reweighing the sample cham-
ber, leaving space for expansion, the assembly was inverted
Since all quantities are known or can be estimated with
and evacuated to remove air and carbon dioxide. The cham-
reasonable accuracy, the values of Csat, the heat capacity
ber was again weighed t o 0.2 gram and the necessary air-
a t thermal saturation for the liquid may be calculated.
buoyancy correction was made. For these experiments the order of magnitude of the various
The entire calorimeter was assembled, and the vacuum quantities is
chamber evacuated and heated to the desired temperature.
A small linear increase in temperature with time was SQ= about 3000 cal.
observed and allowed t o stabilize. K = about 300 ca1.i" C.
A predetermined amount of heat (about 3000 cal.) was M = about 1200 grams
added in 2 minutes. V = about 1400 cc.
Temperatures were observed until the drift was again The sum of the last two terms in Equation 2 which
linear downward. A theoretical analysis is performed on represents the evaporation (or condensation) correction and,
the data to evaluate the hypothetical, instantaneous tem- hence, may be positive or negative has not been over 3
perature rise, and, from it, the heat capacity a t saturation. cal. per C.
248 Journal of Chemical and Engineering Data, Vol. 15, No. 2, 1970
From the values of C,,, the values of the heat capacity
at constant pressure may be calculated directly as
Journal of Chemical and Engineering Data, Vol. 15, No. 2, 1970 249
A similar value for the highest temperature, 2OO0C., and The values from 0" to 80°C. previously reported ( 4 ) were
maximum salinity, 12%, is 0.003. included in the smoothing process.
I n correlating the values, a power series in molality was
RESULTS
used as suggested by Lewis et al. (7); however, as was
found for the data below 80" C. ( 2 ) ,only the two constants
From each value of Cmt measured, a value for C, was and B' were found to be necessary. The standard
calculated and in turn correlated by extended Debye-Huckel deviation was not reduced significantly as more constants
theory. The resulting smoothed C, values are presented were added.
in Table 11. The smoothed saturation heat capacity values, Figure 3 is a graph of the partial heat capacity of the
,C
,, also shown in Table 11, were calculated from C, values. sea salts a t infinite dilution, c,
as a function of tem-
perature. The previously obtained curve to 80°C. ( 2 ) is
included for comparison.
Table I11 is a set of tabular values of C?, B', A,, and
Table Ill. Constants used in Modified Debye-Huckel
qL.
Calculation of Heat Capacities of Sea Water Solutions
Temp.,
The values for A,, c,
and B' were calculated from
Equations 9, 10, and 11, respectively.
c: 7"
%I,- B' A, e;" A, = 7.858661 + 0.04424799t + (0.2129136 x 10-')tZ -
0 -0.7519547 0.2207251 7.859 1.00804
5 -0.6286866 0.1730745 8.131 1.00434 (0.1837382 x 10-'))t3 + (0.7077757 x lO-')t' (9)
10 -0.5326990 0.1384558 8.496 1.00194
15 -0.4591725 0.1131234 8.943 1.00040
20 -0.4039477 0.09444761 9.460 0.99947
25 -0.3634661 0.08057092 10.036 0.99893
30 -0.3347135 0.07017338 10.664 0.99866 --X-- Bromley (2)
35 -0.3151657 0.06231164 11.334 0.99860 -0.2
40 -0.3027379 0.05630773 12.040 0.99869
45 -0.2957356 0.05167180 12.777 0.99889
50 -0.2928088 0.04804805 13.540 0.99919
55 -0.2929087 0.045 17675 14.324 0.99959
60 -0.2952471 0.04286738 15.127 1.00008 9
65 -0.2992585 0.04097953 15.948 1.00065 w
70 -0.3045645 0.03940921 16.786
17.642
1.00132
1.00208
2
V
75 -0.3109415 0.03807911
80 -0.3182903 0.03693145 18.517 1.00299 v)
t1
110 -0.3866099 0.03206476 24.395 1.01074
120 -0.4220917 0.03080604 26.754 1.01448
130 -0.4657488 0.02962081 29.441 1.01888
140 -0.5181096 0.02848113 32.557 1.02403 --0*9
1.0
150 -0.5792712 0.02737002 36.221 1.02998
160 -0.6490865 0.02627704 40.570 1.03683 - 1-1 0 40
170 -0.7275219 0.02519567 45.756 1.04463 Temperature "C.
180 -0.815 1843 0.02412183 51.951 1.05349
190 -0.9140188 0.02305290 59.340 1.06347
1.07467 Figure 3. Partial heat capacities of sea salts at infinite dilution
200 -1.1028176 0.02198723 68.127
for sea water solutions
250 Journal of Chemical and Engineering Data, Vol. 15, No. 2, 1970
cl;" = -0.7519547 + 0.02773842t - (0.6551250 x 1 0 - ' ) t 2 + evaluate enthalpies. The enthalpy values given by the
National Engineering Laboratory Steam Tables (8) were
(0 7890734 X 10 ' ) t ' - (0.5240100 x 10 - ) t 4+
considered correct, and deviations from these were cal-
(0.1756529 X 10 ' ) t ' - (0.2361268 x 10 12)t6 (10) culated by use of heat capacity values contained herein.
B' = -(272) (0.171253 X lo3') T r - 0.072070739 + An estimate was made of the correction to be applied
to the calculated enthalpy values due to the effect of pres-
(1.05884208 x 10 ' ) T (11) sure not allowed for in the evaluation of the enthalpy
of water. This was a maximum a t the highest temperature
These equations were obtained by fitting individual values and salinity and was about 0.01 cal. per gram and, hence,
a t each temperature by the method of least squares. The was neglected. These were combined with values of the
23' values did not fit a simple power function but did relative enthalpies a t 25OC. (3) to give enthalpies. These
fit rather well the form of the equation chosen. Individual were then corrected to refer to O O C . , with the values of
values below 80°C. differ somewhat from those given previ- water and the salts a t infinite dilution being taken to be
ously (2). Part of this resulted from the use of a simple zero. Table VI is the resulting values in calories per gram.
power function to correlate values of A , to 200°C. Values Values in B.t.u. per pound may be approximated by multi-
of and B' were found to be not completely independent. plying by 1.8. Since the B.t.u. is now defined ( I ) using
The values given are the best set found by the computer, the CalorieI, = 4.1868 joules, then strictly to convert from
including the 0" to 80" C. data given previously ( 4 ) . defined calories per gram t o B.t.u. per pound multiply
Values of the apparent and partial values for salts and by 1.8 x (4.1840/4.1868) = 1.8/1.0067.
water are calculated as had been done previously ( 2 ) and Calcium Sulfate. The contents of the calorimeter were
are presented in Tables IV and V. carefully examined after each high temperature run. N o
Enthalpy. Values of the heat capacity, C,, expressed in calcium sulfate or other solid was observed to have precipi-
terms of the heat capacity of pure water, were used to tated from the acidified sea water solutions for all salinities
Table V. Partial Heat Capacities of Salts and Water in Sea Salt Solutions
(Defined calories per gram degree centigrade)
Temp., Salinitv. %
OC. 0 1 2 3 4 5 6 7 8 9 10 11 12
Salts
0 -0.752 -0.633 -0.548 -0.466 -0.385 -0.303 -0.221 -0.137 -0.053 0.034 0.122 0.211 0.303
10 -0.533 -0.436 -0.377 -0.322 -0.269 -0.216 -0.162 -0.108 -0.054 0.001 0.058 0.115 0.173
20 -0.404 -0.316 -0.270 -0.229 -0.189 -0.151 -0.113 -0.075 -0.036 0.003 0.042 0.082 0.123
30 -0.335 -0.247 -0.207 -0.173 -0.141 -0.110 -0.080 -0.050 -0.020 0.010 0.040 0.070 0.101
40 -0.303 -0.211 -0.173 -0.142 -0.114 -0.088 -0.062 -0.037 -0.011 0.014 0.039 0.064 0.090
50 -0.293 -0.194 -0.157 -0.128 -0.101 -0.077 -0.053 -0.030 -0.007 0.015 0.037 0.060 0.083
60 -0.295 -0.189 -0.151 -0.121 -0.096 -0.072 -0.049 -0.028 -0.006 0.015 0.036 0.056 0.077
70 -0.305 -0.189 -0.150 -0.120 -0.094 -0.070 -0.048 -0.027 -0.007 0.014 0.034 0.054 0.073
80 -0.318 -0.193 -0.152 -0.121 -0.095 -0.071 -0.049 -0.028 -0.008 0.012 0.032 0.051 0.070
90 -0.336 -0.200 -0.156 -0.124 -0.098 -0.074 -0.051 -0.030 -0.010 0.009 0.029 0.048 0.067
100 -0.358 -0.211 -0.165 -0.131 -0.104 -0.079 -0.057 -0.035 -0.015 0.005 0.024 0.043 0.061
110 -0.387 -0.227 -0.178 -0.143 -0.114 -0.089 -0.065 -0.044 -0.023 -0.004 0.016 0.035 0.053
120 -0.422 -0.248 -0.196 -0.159 -0.129 -0.102 -0.079 -0.057 -0.036 -0.016 0.004 0.023 0.041
130 -0.466 -0.276 -0.220 -0.180 -0.149 -0.121 -0.097 -0.074 -0.052 -0.032 -0.012 0.007 0.026
140 -0.518 -0.309 -0.249 -0.207 -0.173 -0.144 -0.119 -0.095 -0.073 -0.052 -0.032 -0.012 0.007
150 -0.579 -0.348 -0.282 -0.237 -0.201 -0.171 -0.144 -0.119 -0.096 -0.074 -0.053 -0.033 -0.014
160 -0.649 -0.392 -0.319 -0.270 -0.231 -0.199 -0.170 -0.144 -0.120 -0.097 -0.076 -0.055 -0.035
170 -0.728 -0.439 -0.358 -0.304 -0.262 -0.227 -0.196 -0.168 -0.143 -0.119 -0.096 -0.075 -0.054
180 -0.815 -0.489 -0.399 -0.339 -0.293 -0.254 -0.221 -0.191 -0.164 -0.138 -0.115 -0.092 -0.070
190 -0.914 -0.543 -0.442 -0.375 -0.323 -0.281 -0.244 -0.212 -0.182 -0.155 -0.130 -0.105 -0.082
200 -1.028 -0.604 -0.489 -0.413 -0.356 -0.309 -0.268 -0.233 -0.201 -0.171 -0.143 -0.118 -0.093
Water
0 1.0080 1.0075 1.0063 1.0042 1.0012 0.9974 0.9926 0.9868 0.9799 0.9719 0.9626 0.9521 0.9402
10 1.0019 1.0016 1.0007 0.9993 0.9973 0.9948 0.9917 0.9880 0.9835 0.9784 0.9725 0.9658 0.9582
20 0.9995 0.9992 0.9985 0.9974 0.9960 0.9942 0.9920 0.9893 0.9862 0.9826 0.9784 0.9738 0.9685
30 0.9987 0.9984 0.9978 0.9969 0.9957 0.9943 0.9925 0.9905 0.9880 0.9853 0.9821 0.9785 0.9745
40 0.9987 0.9984 0.9978 0.9970 0.9960 0.9948 0.9933 0.9915 0.9895 0.9871 0.9845 0.9815 0.9782
50 0.9992 0.9989 0.9983 0.9976 0.9966 0.9955 0.9941 0.9925 0.9907 0.9886 0.9862 0.9836 0.9806
60 1.0001 0.9998 0.9992 0.9984 0.9975 0.9964 0.9951 0.9936 0.9918 0.9899 0.9877 0.9853 0.9825
70 1.0013 1.0010 1.0004 0.9996 0.9987 0.9976 0.9963 0.9948 0.9932 0.9913 0.9892 0.9868 0.9843
80 1.0030 1.0026 1.0020 1.0012 1.0003 0.9992 0.9979 0.9964 0.9948 0.9929 0.9909 0.9886 0.9861
90 1.0051 1.0047 1.0040 1.0032 1.0022 1.0011 0.9998 0.9983 0.9967 0.9949 0.9929 0.9906 0.9882
100 1.0076 1.0072 1.0065 1.0057 1.0046 1.0035 1.0022 1.0007 0.9991 0.9972 0.9952 0.9930 0.9906
110 1.0107 1.0103 1.0095 1.0087 0.0076 1.0064 1.0051 1.0036 1.0019 1.0001 0.9981 0.9958 0.9934
120 1.0145 1.0140 1.0132 1.0123 1.0112 1.0099 1.0086 1.0070 1.0053 1.0035 1.0014 0.9992 0.9968
130 1.0189 1.0183 1.0175 1.0165 1.0154 1.0141 1.0126 1.0111 1.0093 1.0074 1.0054 1.0031 1.0007
140 1.0240 1.0234 1.0225 1.0215 1.0202 1.0189 1.0174 1.0158 1.0140 1.0120 1.0099 1.0076 1.0051
150 1.0300 1.0293 1.0283 1.0272 1.0259 1.0245 1.0229 1.0212 1.0193 1.0173 1.0151 1.0128 1.0102
160 1.0368 1.0361 1.0350 1.0338 1.0324 1.0308 1.0292 1.0274 1.0254 1.0233 1.0210 1.0186 1.0160
170 1.0446 1.0438 1.0426 1.0412 1.0397 1.0381 1.0363 1.0343 1.0323 1.0301 1.0277 1.0252 1.0225
180 1.0535 1.0526 1.0512 1.0497 1.0480 0.0462 1.0443 1.0422 1.0400 1.0377 1.0352 1.0325 1.0297
190 1.0635 1.0624 1.0609 1.0592 1.0574 1.0554 1.0533 1.0510 1.0486 1.0461 1.0434 1.0406 1.0376
200 1.0747 1.0735 1.0718 1.0699 1.0678 1.0656 1.0632 1.0608 1.0582 1.0554 1.0525 1.0495 1.0463
Journal of Chemical and Engineering Data, Vol. 15, No. 2, 1970 251
Table VI. Enthalpy of Sea Salt Solutions at Thermal Saturation
(Defined calories per gram)
252 Journal of Chemical and Engineering Data, Vol. 15, No. 2, 1970
Q = electrical heat input, cal. (7) Lewis, G.N., Randall, M., Pitzer, K.S., Brewer, L.,
S = salinity in weight per cent. Approximately per cent total “Thermodynamics,” 2nd ed., p. 642, McGraw-Hill, New York,
solids (see Procedure section for discussion) 1961.
T = temperature, K. (8) “National Engineering Laboratory Steam Tables,” Her
t = temperature, C. Majesty’s Stationery Office, Edinburgh, 1964.
u = specific volume of saturated liquid, cmS3/g. (9) Osborne, N.S., J . Res. Nail. Bur. Std. 4, 609 (1930).
U’ = specific volume of saturated vapor, ~ m . ~ / g . (10) Osborne, N.S., Stimson, H.F., Ginnings, D.C., Ibid.,
V = internal volume of calorimeter, ~ m . ~ 23, 197 (1939).
x = mass fraction of liquid in calorimeter (11) Oxner, M., Knudsen, M., “Determination of Chlorinity by
2, = charge on ion i the Knudsen Method,” G.M. Mfg. CO.,New York, 1962.
01’ ’13 = ( l i r a*) [I + I”* - I / ( I + I”‘) - 2 In(1 + I”’)] (12) Sverdrup, H.U., Johnson, M.W., Fleming, R.H., “The Oceans.
u = standard deviation Their Physics, Chemistry, and General Biology,” 8th printing,
Prentice-Hall, Englewood Cliffs, N. J., 1942.
LITERATURE CITED (13) Wilkins, D.G., M.S. thesis, University of California, Berkeley,
Calif., 1968.
(1) Am. SOC.Mechanical Engineers, United Engineering Center,
New York, “ASME Steam Tables,” 1967.
(2) Bromley, L.A., J. CHEM.ENG.DATA,13, 60 (1968).
(3) Ibid.,p. 399.
(4) Bromley, L.A., De Saussure, V.A., Clipp, J.C., Wright, J.A.,
Ibid.,12, 202 (1967).
(5) Cox, R.A., Smith, N.D., Pmc. Roy. SOC.A252, 51 (1959).
(6) iamieson, D.T., Tudhope, J.S., Morris, R., Cartwright, G., RECEIVED for review August 29, 1969. Accepted February 2, 1970.
Physical Properties of Sea Water Solutions. Heat Capacity,” The authors were aided in this study by a grant from the Office
“Desalination” (to be published). of Saline Water, U. S. Department of the Interior.
Vapor and liquid equilibrium phase comporitions were determined in the ethane-
n-hexane system at 150°, 250°, and 350‘ F. at pressures from approximately 60
p.s.i.9. to near the critical. Phase envelopes were extrapolated to yield critical composi-
tion and pressure at each temperature. Equilibrium ratios (K = y / x ) from the
experimental data are compared with those from the most recent revision of the
NGPSA K-charts. As previous studies of the ethane-n-hexane binary are not found
in the literature, no comparison with other experimental work is possible.
THE
MIXTURES of ethane and n-hexane were confined tions of the average cell temperature from the nominal
over mercury in a 35-ml. windowed stainless steel cell. temperature of each isotherm did not exceed 0.25”F.
T h e equilibrium cell was immersed in a controlled- Pressure measurements were made with 1000- and 5000-
temperature oil bath. By means of a magnetic pump, vapor p.s.i.g. Bourdon tube pressure gages with sensitivities of
from the top of the cell was recirculated through the bottom 0.1% of full scale. These gages were calibrated against
of the cell for 2 to 4 hours, after which from 3 t o 6 a dead-weight pressure gage with calibration traceable to
hours were allowed for complete phase separation. Sampling NBS standards. Uncertainties in the reported experimental
was carried out under constant pressure conditions by sim- pressures ale believed not t o exceed 2 p.s.i. below 1000
ultaneously injecting mercury into the bottom of the cell p.s.i.g. but may be as great as 7.5 p s i . for pressures greater
while the sample was being withdrawn. N o single-phase than 1000 p.s.i.g.
samples were taken; however, in a number of instances, Further details of the apparatus and experimental pro-
insufficient amount of one of the equilibrium phases pre- cedures have been given by Roberts et al. ( 3 ) and Poston
cluded its being sampled. and McKetta ( 2 ) . Recent modifications were described by
The equilibrium temperature was determined from the Zais ( 5 ) .
average indication of four iron-constantan thermocouples
A N A LYT ICAL
a t separate locations near the cell. T h e thermocouple-
potentiometer combination was calibrated against mercury- T h e vapor and liquid phase samples were analyzed by
in-glass thermometers which had been calibrated by the means of a Beckman Model GC-2A gas chromatograph
National Bureau of Standards. T h e accuracy of any equipped with a 6-foot silicone column (Beckman No.
indicated temperature is estimated to be 0.1” F., and devia- 17449). Chromatograms were interpreted by the peak height
Journal of Chemical and Engineering Data, Vol. 15, No. 2, 1970 253