Andon et a1.: Thermodynamic Properties of Phosphorus Compounds.

II 65

The results previously given indicate that ethanol is more
readily accepted into the polymer network and the tendency
to aggregate at hydrophilic centres is thereby greatly re-
duced. Even if some movement of ethanol molecules toward
these boundary layer sites does occur, the capacity for hydro-
gen bond formation being much less than that for water, the
disruptive capacity is reduced.
A convenient indication of hydrogen bonding ability may
be obtained by consideration of the so-called solubility
parameter, 6, of a solvent. This parameter is related to the
cohesive energy density and may be expressed mathematically
as
6 = (AE/V)k
where AE is the energy of vaporisation for a gas at zero
pressure and V is molar volume. The higher the value of 6
the greater the capacity for hydrogen bonding. The res-
pective values for water and ethanol are 2 3 4 and 12.7
(cal/cm3)
I t has been suggested that the decrease in bond strength on
exposure to water vapour can be explained by the move-
ment of condensed water into voids and capillaries present
as defects between the polymer and s ~ b s t r a t e .The
~ authors
cannot accept that such a process could lead to the phenomena
observed. Moreover this route for ingress of the hostile
entity is incompatible with the observation that water (surface
tension 75.6 dynes/cm at 0 ) causes a fall in bond strength
' Patrick, R. L., & Payne, G. O., jun., J. Colloid Sci., 1961, 16,
whereas ethanol (surface tension 24.05 dynes/cm at 0")does
not. If ethanol were to enter the bond system only via the
capillary route, then for rapid uptake by the bulk polymer
to occur, the interface area would require to be completely
saturated with solvent-it is inconceivable that in such con-
ditions no loss of strength would be detected.
Further work is in hand to examine the effect of other
small molecules in an attempt to relate the phenomenon to
such factors as molecular volume, polarity and vapour
pressure.
Acknowledgments
The authors wish to thank the Director, Atomic Weapons
Research Establishment, for permission to publish, and Mr.
W. M. Long and Dr. A. Catherall for helpful discussions.
United Kingdom Atomic Energy Authority,
AWRE,
Aldermaston,
Berks.
Received 28 September, 1966
References
Falconer, D. J., MacDonald, N. C., & Walker, P., Chemy Ind.,
1964, p. 1230
Aircraft Materials Specification DTD 915 B (Ministry of
Aviation)
Lund, H., & Bjerrum, J., Ber. dt. chem. Ges., 1931, 64, 210
4 The Hounsfield Tensometer Manual, Fig. 6, Type 11 (cast),
Tensometer Limited Croydon
93
Patrick, R. L., Doede C. M., & Vaughan, W. A., jun., J. phys.
Chem., Ithaca, 1957, 61, 1036
Grornov, V. K., Neiman, M. B., Vakula, V. L., & Voyutskii,
S. S., Russ. J. phys. Chem., 1963, 37, 1125
8 Polymer Handbook (New York: Interscience), 1965
9 Wake, W. C., Discussions at Fourth Conference on Additives
and Adhesion, April, 1966, The City University, London

THERMODYNAMIC PROPERTIES OF PHOSPHORUS

COMPOUNDS
11". LOW-TEMPERATURE HEAT CAPACITY AND ENTROPY OF
SODIUM MONO-, DI-, AND TRI-PHOSPHATES
By R. J. L. ANDON, J. F. COUNSELL, J. F. MARTIN and C. J. MASH

Heat capacities from 10-320"~of nine sodium phosphates have been measured by adiabatic calorimetry
and the entropies of the compounds have been calculated, The values of S298 found were: NaH2P0430.47;
Na,HP04 35.97; Na,P04 41.54; Na2H,P,0, 52.63; Na4PZ0, 64.60; Na,P,O, 68.47; N a s P 3 0 1 0 ~ 6 H ~ 0
146.1;Na5P3O1,(I) 91.25; Na5P,0,, (11) 87.37 cal/deg. mole. The estimation of thermodynamic propertles
of other sodium phosphates is discussed.

Introduction
phosphoric acid and can be converted into di-, tri-, and poly-
In a recent review of the industrial importance of phos- phosphates by heat treatment. Heats of formation of some
phorus compounds,' the uses of the sodium phosphates in sodium phosphates have recently been measured' but little
food technology and in the synthetic detergent industry were or no data are available on the entropies of the sodium
described. The sodium monophosphates are prepared from phosphates. Measurements have now been made of the low
* Part 1: Trans. Faraday Soc., 1963,59, 2102.
J. Appl. Chem., 1967, Vol. 17, March
66 Andon et d.:Theriiiodynamic Prqmticjs of Phosphorus Compounds. / I
temperature heat capacities of three sodium monophos-
phates (sodium dihydrogen orthophosphate, disodium hy-
drogen orthophosphate and trisodium orthophosphate), two
diphosphates (disodium di hydrogen pyrophosphate and
tetrasodium pyrophosphate), and four triphosphates (sodium
trimetaphosphate, sodium triphosphate hexahydrate, sodium
triphosphate phases 1 and 11).
Experiniental
Materials
All the sodium phosphates were prepared and analysed by
staff of the Research Department of Messrs. Albright and
Wilson Ltd.
Sodium dihydrogen orthophosphate, NaH2POd, and di-
sodium hydrogen orthophosphate, NazHP04, were prepared
by heating the A.R. hydrates at 118". The samples were
shown by paper chromatography to contain less than 0.5
(the smallest detectable amount) of pyrophosphate.
Trisodium orthophosphate, Na,PO,, was prepared by
heating Na,HPO, mixed with Na2C03 at 1000" for several
hours. The product contained 0.9% of Na2C03 and was
9 9 s 1 "/, Na,P04. The X-ray diffraction pattern of the
sample was identical with published data.3
Disodium dihydrogen pyrophosphate, Na2H2P207,was
prepared from A.R. NaH2P04 by heating at 200". X-ray
diffraction showed that the product, which contained a
trace of water-insoluble material, was crystalline and con-
taincd 5.1 % of (NaPO,), as an impurity.
Tetrasodium pyrophosphate, Na4P207, was prepared
from recrystallised A.R. Na4P,0,.10Hz0 by drying at
1 2 0 for seven days. The product contained no impurities
detectable by X-ray diffraction or paper chromatography,
indicating less than 0.5 % of other phosphates. Spectro-
graphic analysis showed that extraneous elements in the
sample amounted to less than 0.3 %.
Sodium trimetaphosphate, Na3P309, was prepared by
heating A.R. NaH,P04.2H,0 at 120" to form the anhydrous
compound which was then heated at 500-550" until the
product was substantially water-soluble. The product was
dissolved in water and filtered to remove insoluble meta-
phosphates. The required compound, precipitated from the
solution by addition of methylated spirits, was dried at
100-120", and reheated to 500". Analysis of the sample
gave the following results: Na/P ratio 1.002; P 2 0 5 69.2%;
N a 2 0 30.1 %. The presence of orthophosphates equivalent
to 0.25 % sodium orthophosphate was found, but neither
pyrophosphate nor triphosphate was detected by paper
chromatography. The sample contained 0.3% of soluble
long-chain metaphosphates but no insoluble long-chain sub-
stances. The sample showed no weight-loss after ignition
to 560". Its X-ray diffraction pattern corresponded with that
for crystalline sodium trimetaph~sphate.~
Sodium triphosphate hexahydrate, Na,P30 I o.6H ,O, pre-
pared from commercial sodium triphosphate by the method
of Q ~ i m b y was
, ~ analysed by paper chromatography and
was found to contain less than 0.5 % sodium orthophosphate.
The presence of pyrophosphates could not be detected. Thc
water content of the sample, determined by heating the
specimen to 500', was found to exceed by 0.33% that re-
quired for the hexahydrate.
Sodium triphosphate, phase I, was prepared by heating the
hexahydrate to 550" and by cooling the product as quickly
as possible to avoid the formation of phase IT. X-ray diffrac-
* A table of the experimental values is available on application to the authors.
tion patterns showed the absence of phase I I and of pyro-
phosphates. One per cent of the phosphorus as pyrophosphate
and less than 0.5% of the phosphorus as orthophosphate
were detected by paper chromatography.
Sodium triphosphate, phase 11, was prepared by heating
the hexahydrate to 340" and the product was shown by
X-ray diffraction analysis to contain 1 % of tetrasodium
pyrophosphate (a corresponding amount of metaphosphate
would be present because of the reaction, Na5P3OIo=
Na4P207SNaPO,), but no sodium triphosphate, phase
I . Paper chromatography also showed the presence of 1 %
of the phosphorus as pyrophosphate and less than 0.50/, as
orthophosphate in the sample.
Measurements
Heat capacities from 10 to 3 2 0 ' ~were measured using
samples of the sodium phosphates sealed into a gold-plated
copper calorimeter, fitted with a platinum resistance thermo-
meter and a heater. The calorimeter was evacuated and,
before sealing off, helium gas (at 3 cm. Hg pressure) was
introduced to promote thcrmal equilibration. A description
of the cryostat used in the measurements and its operation
has been previously p ~ b l i s h e d .Heat
~ inputs were arranged
to give temperature rises of about 5" at temperatures above
5 0 " ~and of about 1-5" below 5 0 ~ .A 0.l-microvolt
potentiometer with a galvanometer amplifier was used for
measurements of the resistance of the platinum thermometer
and for some of the measurements of the voltage and current
of the heater. The duration of the heat input was controlled
and measured by a quartz-crystal timer. The platinum
resistance thermometer, the potentiometer, standard re-
sistance and cells were calibrated in Standards Division,
N.P.L. For some of the compounds, measurements of
voltage and current of the calorimeter heater were made
automatically at one minute intervals during the heat inputs
by a digital voltmeter with a full-scale reading of 2.9999 volts.
The readings of the digital voltmeter and the potentiometer
were recorded by a teleprinter and tape punch. All experi-
mental observations were thus recorded on a punched tape,
from which the heat capacities of the filled calorimeter at
the mean temperature for each heat input were calculated by
computer. The heat capacity of the empty calorimeter was
mcasured in a separate set of experiments.
Results
The experimental heat capacities" were smoothed graphi-
cally and extrapolated to O'K by use of suitable combinations
of Einstein and Debye functions. From the smoothed
values, low-temperature thermodynamic properties were
calculated by computer (Table I). The values for disodium
dihydrogen pyrophosphate were corrected for the presence
of 5 . 1 % of sodium metaphosphate impurity by use of the
heat capacities of Na3P30g reported in Table I. The heat
capacity of sodium triphosphate hexahydrate was corrected
for the presence of 0.33 "/, excess water using published data
for water.6 A correction was also made for sodium carbonate"
impurity in trisodium phosphate. Over most of the tem-
perature range these corrections did not exceed 0.2%. No
corrections were made for impurities in the samples of any of
the other sodium phosphates.
Discussion
The results obtained from the measurements now reported
J. appl. Chem., 1967, Vol. 17,March
 TABLEI
Molar thermodynamic properties of sodium phosphates
Sodium dihydragen orthophosphate, NaHIP04 Disodium hydrogen orthophosphate, NarHPOI Trisodium orthophosphate, Na3PO4

Temp., C,, S, (H-HO), ( H - N " ) / T , -(G-H')'T Temp., CP, s, ( H - H : ) , (H-HE)/T, -(C-H')/T. Tecmp., CP, S, (H-H;), (H-H:)/T, -(G-H,")/T,
'K cal./deg. cal./deg. cal. cal./d&. cal./dei.' ' OK cal./deg. cal./deg. cal. cal./deg. cal./deg. K cal./deg. cal./deg. cal. cal.:deg. cal.ideg.
- -
10.00 0,082 0.027 0.205 0,021 0.007 10.00 0.079 0.026 0.199 0.020 0,006 10.00 0.066 0.022 0.162 0.016 0.005
15.00 0.288 0,093 1.053 0.070 0.023 15.00 0.276 0.089 1.005 0.067 0,022 15.00 0.220 0.073 0.827 0.055 0.018
20.00 0.710 0.228 3.445 0,172 0.056 20.00 0.698 0,220 3.333 0.167 0.053 20.00 0.596 0.182 2.763 0.138 0,044
25.00 1.341 0.451 8.511 0.340 0.111 25.00 1.346 0,441 8.350 0.334 0.107 25.00 1.210 0.377 7.178 0.287 0.090
30.00 2.078 0.760 17.03 0.568 0 192 30.00 2.138 0.755 17.01 0.567 0.188 30.00 2.038 0.668 15.24 0.508 0.160
35.00 2.917 1.142 29.48 0.842 0.300 35.00 3.053 1.152 29.94 0.856 0.296 35.00 3.052 1.056 21.87 0.796 0.259
40.00 3.810 1.590 46.30 1.157 0.432 40.00 4.065 1 ,625 47.70 1.193 0.432 40.00 4.209 1.538 45.98 1.150 0.388
45.00 4,695 2.090 67.56 1.501 0.588 45.OO 5.113 2.164 70-64 1.570 0.594 45.00 5.448 2.104 70.09 1.558 0.547
50.00 5.586 2.630 93.26 1.865 0,765 50.00 6.195 2.758 98.89 1.978 0.780 50.OO 6.755 2.745 100.6 2.011 0.734
60.00 7.308 3.803 157.8 2.631 1.172 60.00 8.360 4.081 171.8 2.863 1.218 60.00 9.467 4.219 181.8 3.030 1 . I89
70.00 8.856 5.048 238.8 3.411 1.637 70.00 10.34 5.521 265.4 3.792 1.729 70.OO 11.97 5,870 289.2 4.132 1.738
80,OO 10.25 6.323 334.4 4.180 2.143 80.00 12.22 7.026 378.4 4.729 2.296 80.00 14.28 7.621 420.6 5.258 2.363
90.00 11.53 7.606 443.5 4.927 2.678 90.00 13.92 8.565 509.2 5.658 2.907 90.00 16.40 9.428 574.2 6.380 3.047
10040 12-71 8,882 564.7 5,647 3.235 100~00 15.43 10.11 656.2 6.562 3.550 100~00 18.28 11.25 747.8 7,478 3.777
110.00 13.80 10.14 697.3 6.339 3.806 110.00 16.82 11.65 817.5 7.432 4.217 110.00 19.99 13.08 939.3 8.539 4.539
120.00 14.84 11.39 840.6 7.005 4.386 120.00 18.13 13.17 992.3 8.269 4.900 120.00 21.55 14.89 1147 9.560 5.327
130.00 15.81 12.62 993.9 7.645 4.972 130.00 19.32 14.67 1180 9.074 5.594 130.00 22.96 16.67 1370 10-54 6,131
140.00 16.73 13.82 1157 8.262 5.562 140.00 20.42 16.14 1378 9,846 6.295 140.00 24.26 18.42 1606 11.47 6.946
150.00 17.64 15.01 1329 8.857 6.152 150.00 21.47 17.59 1588 10.59 6.999 150.00 25.48 20.13 1855 12.37 7.768
160.00 18.49 16.17 1509 9.433 6.742 160.00 22.45 19 .OO 1808 11.30 7.705 160.00 26.59 21.81 2115 13.22 8.594
170.00 19.30 17.32 1698 9.990 7.331 170.00 23.37 20.39 2037 11.98 8.411 170.00 27.63 23.46 2386 14.04 9.420
180.00 20.07 18.45 1895 10.53 7,917 180.00 24.22 21.75 2275 12.64 9.114 180.oo 28.58 25.06 2668 14.82 10.24
190.00 20.82 19.55 2100 11.05 8.500 190.00 25.02 23.08 2521 13.27 9.815 190.00 29.46 26.63 2958 15.57 11.07
200.00 21.57 20.64 2311 11.56 9.080 200' 00 25.81 24.39 2775 13-88 10.51 2 0 0 .00 30.30 28.17 3257 16.28 11.88
210.00 22.28 21.71 2531 12.05 9.656 210.00 26.57 25.67 3037 14.46 11.20 210.00 31.08 29.66 3564 16.97 12.69
220.00 22.96 22.76 2757 12.53 10.23 220'00 27.32 26.92 3307 15.03 11.89 220.oo 31.83 31.13 3878 17.63 13.50
230.00 23.62 23.79 2990 13.00 10.80 230.OO 28.04 28.15 3584 15.58 12.57 230.00 32.55 32.56 4200 18.26 14.30
240.00 24.29 24.81 3229 13.46 11.36 240'00 28.75 29.36 3868 16.11 13.24 240.00 33.24 33.96 4529 18.87 15.09
250.00 24.96 25.82 3476 13.90 11.92 250.00 29.40 30.54 4158 16.63 13.91 250.00 33.90 35.33 4865 19.46 15.87
260.00 25.59 ''26-81 3728 14.34 12.47 260.00 30.02 31.71 4455 17.14 14.57 260.OO 34.51 36.67 5207 20.03 16.64
270.00 26.21 27.79 3988 14.77 13.02 270.00 30.64 32.85 4759 17.62 15.23 270.00 35.10 37.98 5555 20.57 17.41
273.15 26.41 28.09 4071 14.90 13.19 273.15 30.83 33.21 4856 17.78 15.43 273.15 35.29 38.39 5666 20.74 17.64
280.00 26.82 28.75 4253 15.19 13.56 280.00 31.25 33.98 5068 18.10 15.88 280.00 35.68 39.27 5909 21'10 18.17
290.00 27.43 29.70 4524 15.60 14.10 290.00 31.85 35.09 5384 18.56 16.52 290.00 36.24 40.53 6268 21.62 18.92
298.15 27.93 30.47 4750 15.93 14.54 298.15 32.34 35.97 5646 18.94 17.04 298.15 36.68 41.54 6566 22.02 19.52
300.00 28.03 30.64 4801 16.00 14.64 300.00 32.45 36.18 5705 19.02 17.16 300.00 36-78 41.77 6634 22.11 19.60
310.00 28.65 31.57 5085 16.40 15.17 310.00 33.04 37.25 6033 19.46 17.79 310.00 37.30 42.98 7004 22.59 20.39
320.00 29.23 32.49 5374 16.79 15.70 320.00 33.62 38.31 6366 19.89 18.41 320.OO 37.78 34.18 7379 23.06 21.12
 TABLEI-contd.
Molar thermodynamic properties of sodium phosphates
Sodium triphosphate hexahydrate, NaSP3OL
o.6H*O Sodium triphosphate, N a 5 P , 0 1 0 , phase I Sodium triphosphate, Na5P3OI0,phase I1

Temp., CP, S, ( H - H:), ( H - H')/T, - ( G - H')/T: Temp., Cp, S, ( H - H ; ) , ( H - H : ) / T , --(G-H,O)IT. Temp., C,, S, (H-H:), [H-Hz)/T, -(G-H")/T,
OK cal./deg. cal./deg. cal. cal./d&. cal./dei. OK cal./deg. cal./deg. cal. cal./deg. cal./deg. 'K cal./den. cal./deg. cal. cal./deg. cal./dei.

10.00 0,478 0.160 1.203 0.120 0,040 10.00 0.310 0.104 0.777 0,078 0.026 10.00 0.265 0.088 0,663 0.066 0.022
15.00 1.562 0.536 6.017 0.401 0.135 15.00 1,050 0.349 3.920 0.261 0.087 15.00 0.896 0.307 3.463 0,231 0.076
20.00 3.297. 1.210 17.94 0.897 0.313 20.00 2,350 0.818 12.24 0.612 0.206 20.00 2,050 0.710 10.62 0,531 0.180
25.00 5,678 2.192 40.16 1.606 0.585 25.00 4.155 1.527 28.28 1.131 0.396 25 .00 3.628 1.331 24.67 0.987 0.344
30.00 8.576 3.478 75.65 2.522 0.956 30.00 6.375 2,477 54.52 I ,817 0.660 30.00 5.502 2.154 47.39 1.580 0.575
35 .00 12.01 5.051 126.9 3.626 1.425 35.00 8.749 3.637 92.28 2.637 1 .Ooo 35.00 7.674 3.160 80,17 2.290 0.870
40.00 15.81 6.902 196.4 4.910 1.991 40.00 11.30 4.970 142.3 3.558 1.412 40.00 10.03 4.338 124.4 3.110 1.228
45.00 19.69 8.989 285.2 6.338 2.651 45.00 13.86 6.449 205.2 4.561 1,888 45.00 12.45 5.659 180.6 4.013 1.646
50.00 23.94 11.28 394.2 7.884 3.398 50.00 16.44 8,042 281.0 5.620 2.423 50.00 14.96 7,099 249.1 4.981 2,118
60.00 32.42 16.40 676 5 11.27 5.130 60.00 21.63 11.50 471.3 7,856 3.643 60.00 20.08 10.28 424.5 7.075 3.209
70.00 40.19 22.00 1040 14.86 7.136 70.00 26.53 15.21 712.5 10.18 5,028 70.00 24.81 13.74 649.3 9.275 4.464
80.00 47.66 27.85 1480 18.49 9.357 80.00 31 .OO 19.05 1000 12.51 6.539 80.00 29.21 17.34 919.6 11.49 5.848
90.00 54.51 33.87 1991 22.12 11.75 90.00 35.11 22.94 1331 14.79 8.145 90.00 33.34 21.03 1233 13.70 7.329
100.00 60.68 39.94 2567 25.67 14.26 100.00 38.84 26.83 1701 17.01 9.819 100.00 37.10 24.74 1585 15.85 8.884
110~00 66.48 45.99 3203 29.12 16.87 110~00 42.39 30.70 2108 19.16 11.54 110.00 40.58 28.44 1974 17.94 10.49
120.00 72.05 52.02 3896 32.47 19.55 120.00 45.75 34.54 2548 21.24 13.30 120.00 43.80 32.11 2396 19.97 12.14
130.00 77.18 57.99 4643 35.71 22.28 130.00 48.85 38.32 3022 23.24 15.08 130.00 46.76 35.73 2849 21.91 13.82
140.00 82.13 63.89 5439 38.85 25.04 140.00 51.73 42.05 3525 25.18 16.87 140.00 49.49 39.30 3330 23.79 15.51
150.00 86.64 69.71 6283 41.88 27.82 150 .OO 54.48 45.71 4056 27.04 18.67 150.00 52.12 42.80 3838 25.59 17.21
160.00 91.12 75.44 1172 44.82 30.62 160.00 57.03 49.31 4614 28.83 20.48 160.00 54.57 46.25 4372 27.32 18.92
170.00 95.26 81.09 8104 47.67 33.42 170.00 59.27 52.84 5195 30.56 22.28 170.00 56.84 49.62 4929 29 .OO 20.63
180.00 99.30 86.65 9077 50.43 36.23 180.00 61.15 56.28 5798 32.21 24.07 180.00 58.94 52.93 5508 30.60 22.33
190 .OO 103.2 92.13 10090 53.10 39.03 190.00 62.79 59.63 6418 33.78 25.85 190.00 60.90 56.17 6108 32.14 24.03
200~00 106.9 97.51 11140 55.70 41.82 200.00 64.28 62.89 7053 35.26 27.62 200.00 62.76 59.34 6726 33.63 25.71
210.00 110.3 102.8 12230 58.22 44.59 210.00 65.79 66.06 7703 36.68 29.38 210.00 64.54 62.45 7363 35.06 27.39
220.00 113.8 108.0 13350 60.66 47.36 220.00 67.35 69.16 8369 38.04 31.12 220.00 66.28 65.49 8017 36.44 29.05
230.00 117.1 113.2 14500 63.05 50.11 230.00 68.92 72-19 9050 39.35 32.84 230.00 67.98 68.48 8688 37.77 30.70
240.00 120.4 118.2 15690 65.37 52.84 240'00 70.44 75.15 9747 40.61 34.54 240.00 69.57 71.40 9376 39.07 32.34
250.00 123.6 123.2 16910 67.64 55.56 250.00 71.85 78.06 10460 41.83 36.22 250.00 71.08 74.27 10080 40.32 33.96
260.00 126.5 128.1 18160 69.85 58.25 260.00 73.17 80.90 11180 43.01 37.89 260.00 72.53 77.09 10800 41.53 35.56
270.00 129.3 132.9 19440 72 .00 60.93 270.00 74.47 83.69 11920 44.15 39.53 270.00 73.95 79.85 11530 42.70 37.15
273.15 130.2 134.4 19850 72.67 61.75 273.15 74.88 84.55 12160 44.51 40.03 273.15 74.40 80.71 11760 43.07 37.64
280.00 132.1 137.7 20750 74.09 63.59 280.00 75.77 86.42 12670 45.26 41 '16 280.00 75.33 82.57 12280 43.84 38.73
290.00 134.9 142.4 22080 76.14 66.22 290.00 77.07 89.10 13440 46.34 42.76 290.00 76.67 85.24 13040 44.95 40.28
298.15 137.1 146.1 23190 77.78 68.34 298.15 78.16 91.25 14070 47.19 44.05 298.15 77.72 87.37 13670 45.84 41.53
300.00 137.6 147.0 23440 78.14 68.84 300.00 78.40 91.73 14210 47.38 44.35 300.00 77.95 87.86 13810 46.03 41.83
310.00 140.0 151.5 24830 80.10 71.43 310.00 79.72 94.33 15010 48.40 45.92 3 10 .OO 79.16 90.43 14590 47.08 43.35
320.00 142.6 156.0 26240 82.02 74.00 320.00 8 1.06 96.88 15810 49.40 47.47 320 .OO 80.31 92.96 15390 48.10 44.86
 I-contd.
TABLE
Molar thermodynamic properties of sodium phosphates
Disodium dihydrogen pyrophosphate, Na2H2P207 Tetrasodium pyrophosphate, N a4 PZ0 7 Sodium trimetaphosphate, Na3PiOs
~ ~~ ~ ~~

Temp., C,, S, (H-H:), (H-H,")/T, -(G-Ho)IT, Temp.. CP, S, (H-H,"), ( H - f f Z W , -(G-H:)/T, Tepp., C,, S, (H-H:), (H-H")/T, -(G-H'))'T
OK cal./deg. cal./deg. cal. cal./deg. cal./dei. 'K cal./deg. cal./deg. cal. cal./deg. cal./deg. K cal./deg. cal.ideg. cal. cal.id&. cal./dei. '
~
'-
10.00 0.147 0.048 0.366 0.037 0.012 10.00 0.136 0.045 0,342 0,034 0.011 10.00 0,238 0.080 0.595 0,060 0.020
15.00 0.480 0.164 1.845 0,123 0.041 15.00 0.473 0.155 1.749 0.117 0.038 15.00 0,794 0.267 2.995 0.200 0.067
20.00 1 .I95 0.392 5,888 0.294 0,097 20 .oo 1.192 0.380 5.747 0.287 0,093 20.00 1.775 0.621 9.263 0.463 0,158
25.00 2.226 0.764 14.33 0.573 0.191 25 .OO 2.256 0.754 14.22 0.569 0.185 25.00 3.082 1.152 21.29 0.852 0.300
30.00 3,497 1,278 28.53 0.951 0,327 30.00 3,674 1.286 28.93 0.964 0.322 30.00 4.636 1.848 40.50 1.350 0.498
35.00 4.954 1.925 49.59 1,417 0.508 35.00 5.272 1.971 51.23 1.464 0.507 35.00 6.378 2.692 67.99 1.943 0.750
40.00 6.488 2.686 78.17 1.954 0,732 40.00 7,023 2.787 81.90 2.047 0.740 40.00 8.180 3,661 104.4 2.609 1.052
45.00 8.074 3.541 114.5 2.545 0.995 45 .oo 8.852 3,719 121.5 2.701 1,018 45.00 10.02 4.731 149.9 3.330 1.400
50.00 9.683 4.474 158.9 3.178 1.296 50.00 10.78 4.750 170.6 3.411 1.339 50.00 11.91 5.884 204.7 4.093 1.790
60.00 12.75 6.512 271.2 4.519 1.993 60.00 14.73 7.066 298.2 4.970 2.096 60.00 15.65 8.387 342.6 5.709 2.678
70.00 15.49 8.688 412.7 5.895 2.793 70.00 18.35 9.613 463.9 6.627 2,986 70.00 19.20 11.07 517.1 7.386 3,684
80.00 17.93 10.92 580.0 7.250 3.669 80.00 21.78 12.29 664.7 8.309 3.981 80.00 22.47 13.85 725.6 9.070 4.780
90.00 20.15 13.16 770.6 8.562 4.599 90.00 25 .OO 15.04 898.9 9,988 5.057 90.00 25.50 16.67 965.7 10.73 5.945
100.00 22.17 15.39 982.3 9.823 5.567 100.00 27.84 17.83 1163 11.63 6.194 100.00 28.30 19.51 1235 12.35 7,159
110.00 24.07 17.59 1214 11.03 6.560 110.00 30.43 20.61 1455 13.23 7.378 110~00 31.00 22.33 1531 13.92 8.411
120.00 25.88 19.77 1463 12.20 7.570 120.00 32.84 23.36 1771 14.76 8.596 120.00 33.56 25.14 1854 15.45 9.688
130.00 27.56 21.90 1731 13.31 8.591 130.00 35.09 26.08 2111 16.24 9.836 130.00 35.95 27.92 2202 16.94 10.98
140.00 29.13 24.00 2014 14.39 9.617 140.00 37.14 28.75 2473 17.66 1I .09 140.00 38.20 30.67 2573 18.38 12.29
150.00 30.64 26.07 2313 15.42 10.65 150 .OO 39.04 31.38 2854 19.02 12.36 150.00 40.32 33.38 2966 19.77 13.61
160.00 32.09 28.09 2627 16.42 11.67 160.00 40.82 33.96 3253 20.33 13.63 160.00 42.32 36.05 3379 21.12 14.93
170.00 33.45 30.08 2955 17.38 12.70 170.00 42.50 36.48 3670 21.59 14.90 170.00 44.21 38.67 3812 22.42 16.25
180.00 34.75 32.03 3296 18.31 13.72 180.00 44.07 38.96 4103 22.79 16.17 180 .OO 46.00 41.25 4263 23.68 17.56
190.00 35.98 33.94 3649 19.21 14.73 190.00 45.50 41.38 4551 23.95 17.43 190.00 47.68 43.78 4731 24.90 18.88
200.00 37.17 35.81 4015 20.08 15.74 200.00 46.86 43.75 5013 25.06 18.69 200~00 49.25 46.27 5216 26.08 20.19
2 1 0 ~ 0 0 38.35 37.66 4393 20.92 16.74 210.00 48.16 46.07 5488 26.13 19.93 210 .oo 50.79 48.71 5716 27.22 21.49
220'00 39.46 39.47 4782 21.74 17.73 220.00 49.39 48.34 5975 27.16 21.17 220.00 52.30 51.10 6232 28.33 22.78
230.00 40.56 41.24 5182 22.53 18.71 230.00 50.60 50.56 6475 28.15 22.40 230.00 53.74 53.46 6762 29.40 24.06
240.00 41.64 42.99 5593 23.30 19.69 240.00 51.78 52.74 6987 29.11 23.62 240.00 55.12 55.78 7306 30.44 25.33
25040 42.67 44.71 6014 24.06 20.66 250.00 52.91 54.87 7511 30.04 24.83 250.00 56.42 58.05 7864 31.46 26.60
260.00 43.67 46.41 6446 24.79 21.61 260.00 53.96 56.97 8045 30.94 26.03 260.00 57.61 60.29 8434 32.44 27.85
270.00 44.66 48.07 6888 25.51 22.56 270.00 54.95 59.02 8590 31.81 27.21 270'00 58.74 62.49 9016 33.39 29.09
273.15 44.98 48.59 7030 25.74 22.85 273.15 55.26 59'66 8765 32.09 27.57 273.15 59.09 63'16 9203 33.69 29.47
280.00 45.63 49.72 7339 26.21 23.50 280.00 55.91 61.04 9144 32.66 28.38 280.00 59.88 64.64 9609 34.32 30.32
290.00 46.58 51.33 7800 26.90 24.44 290.00 56.86 63.02 9708 33.48 29.54 290.00 61.06 66.76 10210 35.22 31.54
298.15 47.36 52.63 8184 27.45 25.18 298.15 57.63 64.60 10180 34.13 30.47 298.15 62.00 68.47 10720 35.94 32.52
300.00 47.53 52.93 8271 27.57 25.36 300 .OO 57.80 64.96 10280 34.27 30.69 300.00 62.20 68.85 10830 36.10 32.75
310.00 48.47 54.50 8751 28.23 26.27 310.00 58.68 66.87 10860 35.04 31.83 310.00 63.26 70.91 11460 36.96 33.95
320.00 49.39 56.06 9240 28.88 27.18 320.00 59.54 68.75 11450 35.80 32.95 320.00 64.19 72.93 12100 37.80 35.14
 A d o i i et a1.: Therinodynamic Properries of Pliosphorus Coinpounds. II
TABLE11
Group contributions per gram formula weight for estimation of properties of sodium phosphates

Temperature
OK Na20 P~OS H20 Na,O P,O, H,O Na,O P,O, H,O
- -__ ___-
60 4.261 6.205 2.110 1,423 4.257 0.948 1.131 2.720 0.703
80 6.787 8.192 2.792 3.012 6.308 1.657 2.241 3.840 1.145
I00 8.870 10.000 3.263 4.763 8.330 2.331 3.370 4.889 1.525
I20 10.380 11.983 3.612 6.531 10.311 2.960 4.421 5.900 1.846
140 11.545 13.905 3.915 8.222 12.304 3.536 5.357 6.913 2.118
I 60 12,509 15.676 4.267 9.824 14.287 4.079 6.194 7.896 2.367
I80 13.271 17.362 4.588 11.343 16.229 4.609 6.941 8.852
- ___ 2-598
200 13.903 18.884 4.971 12.780 18.132 5.iio 7.602 9.787 2.816
220 14.413 20.399 5.335 14.134 19.996 5.603 8.201 10.681 3.025
240 14.890 21.804 5.723 15.405 21.839 6.077 8.739 11.548 3.235
260 15.345 23,022 6.149 16.614 23.634 6.555 9.232 12.383 3.442
280 15.764 24.137 6.608 17.767 25.380 7.028 9.679 13.189 3.652
300 16.093 25.352 7.043 18.866 27.086 7.498 10.097 13.958 3.861
320 16.444 26.342 7.578 19.919 28.750 7.971 10.483 14.705 4.073
298.15 16.060 25.253 7.000 18.762 26.936 7.452 10.061 13.888 3.842

may be of use for obtaining reliable estimates of the thermo-
dynamic properties of other sodium phosphates. Methods
of estimation of entropy values have been proposed by
Latimer7 who has given tables of entropy contributions of
elements and negative ions in solid compounds. The values
from Latimer's tables for the entropies at 2 9 8 " ~of sodium
dihydrogen phosphate and trisodium phosphate are 30.3 and
46.5 cal/deg. mole respectively. The first value is in good
agreement with the value at 2 9 8 . 1 5 " ~shown in Table I.
Heat contents of sodium titanates have been calculateds by
addition of the heat contents of the constituent oxides, viz.
NazO and TiO,. If a similar scheme is applied to the en-
tropies at 2 9 8 " ~of the sodium phosphates using a value of
SZ9* for Na,O of 18.2k1 cal/deg. mole6 and for P2OS
of 27.35 cal/deg. the values of s 2 9 8 for four of the
phosphates (Na3PO4 = 1 1Na20.;P205, 41 .O; Na4PZ07=
2Na20.P205,63.8; Na3P309 = l ~ N a 2 0 . 1 ~ P 2 O68.3; 5 , and
Na5P3OiO= 2&Na20.1&P205,86.5 cal/deg. mole) differ
from the experimental values by 0.2-043 cal/deg. mole.
Better values for the contributions of NazO and P z 0 5 groups
to any of the thermodynamic properties of the basic phos-
phates can be obtained by a least squares calculation using all
the data of Table I. Furthermore, the method of estimation
can be extended to acidic phosphates by a similar calculation
of the contributions of H,O from the data in Table I for the
three acidic phosphates considered as +Na20.gPz05.H20,
Na20.&P205.SH20,and Naz0.P205.Hz0. These calcula-
tions were done by computer to obtain group contributions
to C,, S and ( H - H,")/T over the temperature range 60" to
3 2 0 " ~(Table 11). In the temperature range 160" to 3 2 0 ~ ,
the maximum deviations between experimental (Table I)
and calculated (from Table 11) values of heat capacity or
entropy of the basic phosphates were 0.6 %. Slightly greater
differences (1 % for S and 2 % for C,) were observed be-
tween experimental and calculated values for the acidic
phosphates. At 2 9 8 " ~ , the experimental and calculated
values of the entropy of the basic phosphates agreed to
0.2% or better, whilst, for the acidic phosphates, the agree-
ment was within 1%. It is considered that Table I1 will give
reliable estimates of the properties of the higher chain
sodium polyphosphates. The agreement between experi-
mental (68.47 cal/deg. mole) and calculated (68.55) values of
s298 for the ring compound, Na3P309, suggests that the
group contributions of Table I1 may be applicable also to
the ring phosphates, in which case entropies obtained from
Table I1 can be used for calculations of ring-chain equilibria
in the sodium phosphate series.
Acknowledgment
The authors wish to express their thanks to the Research
Department of Messrs Albright & Wilson Ltd. for supplying
samples of the sodium phosphates.
Chemical Standards Division,
National Physical Laboratory,
Teddington, Middlesex
Received 12 September, 1966
References
Childs, A. F., Chemy. Ind., 1965, p. 1006
Meadowcroft, T. R., & Richardson, F. D., Trans. Faratlay
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Quimby, 0. T., J. phys. Chem., Ithaca, 1954, 58, 603
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Kelley, K. K., & King, E. G., Bull. U.S. Bur. Mines, 1961, No.
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J. appl. Chem., 1967, Vol. 17, March