ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2009, Vol. 83, No. 3, pp. 327–333. © Pleiades Publishing, Ltd.

, 2009.
Original Russian Text © K.S. Gavrichev, M.A. Ryumin, A.V. Tyurin, V.M. Gurevich, L.N. Komissarova, A.V. Khoroshilov, G.A. Sharpataya, 2009, published in Zhurnal Fizicheskoi
Khimii, 2009, Vol. 83, No. 3, pp. 407–413.

CHEMICAL THERMODYNAMICS
AND THERMOCHEMISTRY

A Calorimetric Study of the Thermodynamic Properties

of Potassium Molybdate
K. S. Gavricheva, M. A. Ryumina, A. V. Tyurina, V. M. Gurevichb, L. N. Komissarovac,
A. V. Khoroshilova, and G. A. Sharpatayaa
a Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
b Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences,
ul. Kosygina 19, Moscow, 117975 Russia
c Faculty of Chemistry, Moscow State University, Moscow, 119889 Russia

e-mail: TAC@igic.ras.ru
Received December 24, 2007

Abstract—The low-temperature heat capacity of K2MoO4 was measured by adiabatic calorimetry. The
smoothed heat capacity values, entropies, reduced Gibbs energies, and enthalpies were calculated over the tem-
perature range 0–330 K. The standard thermodynamic functions determined at 298.15 K were C °p (298.15 K) =
143.1 ± 0.2 J/(mol K), S°(298.15 K) = 199.3 ± 0.4 J/(mol K), H°(298.15 K)–H°(0) = 28.41 ± 0.03 kJ/mol, and
Φ°(298.15 K) = 104.0 ± 0.4 J/(mol K). The thermal behavior of potassium molybdate at elevated temperatures
was studied by differential scanning calorimetry. The parameters of polymorphic transitions and fusion of
potassium molybdate were determined.
DOI: 10.1134/S0036024409030017

INTRODUCTION entropy S°(298.15 K), enthalpy, and Gibbs energy of

Currently, potassium molybdate has been exten-
sively used in the synthesis of promising materials.
Data on its thermodynamic properties necessary for
technological calculations are, however, either absent
or contradictory. Handbook [1] contains its estimated
formation and the thermal characteristics of phase tran-
sitions. We were unable to find information about the
heat capacity of the compound.
The thermal and X-ray analysis data suggest the fol-
lowing scheme of potassium molybdate reversible
phase transitions:

kIV ( monocl. ) 589 ± 10 K

kIII ( rhomb. ) 723 ± 5 K
kII ( hex. ) 749 ± 10 K kI ( hex. ) 1199 ± 1 K l
δ γ β α

Averaged phase transition temperatures taken from [1]
are given in this scheme. The enthalpies of solid-state
phase transitions were determined by differential ther-
mal analysis (DTA) [2, 3], and the enthalpies of fusion,
by DTA [2] and mixing microcalorimetry [4]. The
structures of potassium molybdate polymorphs were
reported in [5–10]. It was found in [9] that the transition
from the low-temperature phase IV polymorph to the
high-temperature hexagonal phase I occurred through
two intermediate modulated structures (orthorhom-
bic (III) and hexagonal (II)).
An analysis of the literature data showed that the
spread of transition temperatures could depend not only
on the synthetic procedure and storage of K2MoO4
samples but also on experimental techniques. For
instance, the kIV kIII transition was observed at
562 ± 6 K (mean of two measurements) and 598 ± 2 K
(mean of seven measurements) and even at 603–623 K
in several works. Such a spread is also observed in
structural studies. For instance, according to [7], the
monoclinic phase is stable below 578 ± 10 K, whereas,
according to [9], it exists over the temperature range
83–593 K (the accuracy of temperature measurements
was ±5 K). The enthalpies of the kIV kIII and
kIII kII transitions obtained in [2, 3] on different
differential thermal analysis units differ by 30 and 60%,
respectively. No calorimetric studies of polymorphic
transitions have been reported.
This work continues studies of alkali metal molyb-
dates [11]. It is concerned with the low-temperature
(10–330 K) heat capacity of potassium molybdate mea-
sured to obtain reliable thermodynamic property val-
ues. We also determined the thermal parameters of

327
328 GAVRICHEV et al.

Table 1. Crystallographic data on potassium molybdate polymorphs and sodium and rubidium molybdate low-temperature
forms
Compound Space group Unit cell parameters (Å, deg) Refs.
K2MoO4 (kIV) C2/m a = 12.345, b = 6.078, c = 7.535, β = 115.73 [5, 6]
K2MoO4 (kIII) Ccmm a = 10.933, b = 6.312, c = 7.944 [10]
K2MoO4 (kII) P 3 m1 a = 6.316, c = 7.959 [9]
K2MoO4 (kI) P 3 m1 a = 6.331, c = 8.07 [7–9]
K2MoO4 C2/m a = 12.338(3), b = 6.080(3), c = 7.528(3), β = 115.68 This work
Na2MoO4 Fd3m 9.108 [12]
Rb2MoO4 C2/m a = 12.841, b = 6.253, c = 7.842, β = 115.64 [6]

phase transitions by differential scanning calorimetry
(DSC).
EXPERIMENTAL
Synthesis. Potassium molybdate was prepared by
calcining stoichiometric amounts of K2CO3 (kh. ch.
(chemically pure) grade) and MoO3 (kh. ch. grade) at
473, 773, and 973 K for 24 h at each temperature.
Unlike sodium molybdate, which has a cubic structure
at room temperature [12], potassium molybdate, like
rubidium molybdate, crystallizes in the monoclinic sys-
tem (Table 1). The diffractogram of the sample
obtained did not contain reflections of impurity phases.
Low-temperature region. Heat capacity was mea-
sured on a BKT-3 adiabatic vacuum calorimeter
designed and manufactured at AOZT “Termis” (Men-
deleevo, Moscow oblast). A detailed description of the
instrument and procedure for measurements was given
in [13]. The temperature of the sample was measured
by an iron–rhodium resistance thermometer (R ≈ 100 Ω).
The sensitivity of the thermometric circuit was 1 × 10–3 K,
and the absolute error in temperature measurements
was ±5 × 10–3 K. The International Temperature Scale
ITS-90 was used for temperature measurements. Stan-
dard substance (benzoic acid K-2 brand) measurements
showed that the error in heat capacity values was ±2%
at helium temperatures, decreased to ±0.4% as the tem-
perature increased to 40 K, and was ±0.2% over the
temperature range 40–350 K.
To verify the results, we performed additional mea-
surements on an adiabatic calorimeter with a TSPN-2V
platinum resistance thermometer calibrated at the
Research Institute of Physicotechnical and Radiotech-
nical measurements against a standard resistance ther-
mometer. The design of this calorimeter was described
in detail in [14]. The energy released in the calorimeter
and the temperature of the sample were measured using
a potentiometric circuit. The accuracy of temperature
measurements was ±10–2 K. The measuring circuit of
the resistance thermometer allowed values to be
obtained with an accuracy of 0.1 µV (0.0005 K at 273 K
and 0.001 K at 15 K). The voltage drop in measure-
ments of the energy released in the heater of the calo-
rimeter was determined to within 1 µV.
Before placing it into a container, the sample was
ground to a particle size less than 1 mm to reduce the
time of temperature leveling in the calorimeter during
measurements under step heating conditions. After the
evacuation of the calorimetric container, it was filled
with a heat exchanging gas (helium) to a pressure of
104 Pa and sealed. Potassium molybdate samples were
loaded into the container in air. The weight of the sam-
ples was 1.1451 g (the main measurements) and 1.1457 g
(control measurements). The molecular weight of
ä2MoO4 was taken to be 238.1342 g/mol [15].
High-temperature region. We used METTLER
TA4000 (the accuracy of temperature measurements
±0.2 K, power detection threshold 160 µW, error in
enthalpy measurements 2%) and SETARAM DSC
2000 K (power and energy detection thresholds 100 µW
and 1 mJ, respectively) units. Our calibration against
metallic standards showed that, for the SETARAM
DSC 2000 K calorimeter, measurement errors were
±2.5 K for temperature and 4–10% for the enthalpy of
thermal effects depending on the temperature interval.
On the SETARAM calorimeter, the sample and ref-
erence (Al2O3 powder calcined in air) were placed into
open alundum crucibles with a volume of 0.1 cm3. On
the METTLER calorimeter, not sealed aluminum cap-
sules with a volume of 0.04 cm3 were used. The sam-
ples were weighed before and after experiments with an
accuracy of 0.0001 g. To prevent possible reactions
between the samples and air oxygen at high tempera-
tures and protect equipment, measurements were taken
in an inert dynamic gas medium. High-purity argon (Ar
no less than 99.998%) was used as a carrier gas; its flow
rate was 0.5–0.75 l/h.
The thermal properties of finely crystalline potas-
sium molybdate were studied on the METTLER unit
over the temperature range 473–773 K at heating/cool-
ing rates of 5 K/min and on the SETARAM unit over
the temperature range 473–1373 K at heating rates of
5 and 10 K/min with subsequent cooling at a rate of
10 K/min to 523 and 293 K, respectively.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 3 2009

 A CALORIMETRIC STUDY OF THE THERMODYNAMIC PROPERTIES 329

Table 2. Experimental heat capacities of K2MoO4, J/(mol K)

T, K Cp T, K Cp T, K Cp T, K Cp

1 series 172.42 117.1 23.85 13.15 204.50 125.7

78.83 73.28 174.89 117.8 25.34 14.94 210.28 127.0
81.32 75.66 177.36 118.5 26.86 16.77 216.06 128.1
83.37 76.83 179.82 119.2 28.39 18.72 221.83 129.4
85.43 78.02 182.29 119.8 29.93 20.67 227.59 130.7
87.48 80.21 184.75 120.5 31.49 22.80 233.34 131.7
89.53 81.76 187.21 121.2 33.05 24.87 239.07 132.8
91.59 82.95 189.67 121.8 34.62 26.67 244.80 133.9
93.65 84.15 192.13 122.4 36.20 28.86 250.52 135.0
95.72 85.32 194.59 123.1 37.78 31.10 256.21 136.0
97.78 86.50 197.05 123.7 39.38 33.14 261.90 137.1
99.84 87.63 199.51 124.3 40.97 35.16 267.56 138.2
102.52 88.94 202.38 125.0 42.58 37.16 273.08 139.0
105.80 90.84 205.65 125.7 44.20 39.18 278.69 140.0
109.09 92.60 208.92 126.2 45.84 41.24 284.28 141.1
112.38 94.28 212.19 126.9 47.46 43.36 289.85 141.9
115.68 95.81 215.40 127.5 49.09 45.35 295.44 142.9
118.99 97.42 3 series 50.72 47.29 300.99 143.8
122.29 98.95 8.97 .0924 52.34 49.31 307.27 144.7
125.59 100.4 9.38 .2568 53.98 51.10 313.54 145.3
2 series 9.80 .4331 55.62 52.84 318.56 146.0
132.27 103.2 10.31 .8805 57.26 54.53 323.54 146.6
135.34 104.3 10.94 1.290 58.91 56.17 328.45 147.2
137.82 105.2 11.59 1.824 60.55 57.87 333.32 147.7
140.29 106.2 12.28 2.306 62.21 59.39 338.14 148.1
142.76 107.2 12.97 2.728 63.86 60.97 342.90 148.2
145.24 108.1 13.68 3.127 65.52 62.45 5 series
147.71 109.0 14.40 3.601 67.18 63.90 245.21 135.4
150.18 110.0 15.13 4.179 68.84 65.30 249.24 136.2
152.65 110.7 15.88 4.777 70.51 66.68 253.29 134.8
155.12 111.6 16.63 5.444 72.60 68.33 257.31 136.6
157.60 112.3 17.38 6.162 75.08 70.44 6 series
160.07 113.4 18.15 6.875 4 series 99.83 86.47
162.54 114.1 18.91 7.665 174.38 118.0 102.61 87.67
165.01 114.9 19.69 8.485 182.33 120.3 106.02 89.81
167.48 115.6 20.91 9.812 190.13 122.4 109.60 92.30
169.95 116.4 22.36 11.47 197.80 124.3 112.96 94.45
116.16 95.26

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 3 2009

330 GAVRICHEV et al.

Table 3. The smoothed thermodynamic functions of K2MoO4 RESULTS AND DISCUSSION

over the temperature range 0–330 K (∆H° in J/mol and the
other functions in J/(mol K)) The experimental data on the heat capacity of
K2MoO4 are listed in Table 2. The results of addi-
T, K C °p (T) S°(T) H°(T)–H°(0) Φ°(T) tional measurements (Table 2, series 5 and 6) satis-
factorily coincided with those of the main measure-
9 .847 .283 1.925 .0693 ments (Table 2, series 1–4). The experimental temper-
10 1.156 .3881 2.927 .0954 ature dependences of heat capacity were smoothed by
12 1.993 .6688 6.040 .1654 the equation
14 3.140 1.058 11.13 .2631 3

∑ a D ( θ /T )
1
C °p ( T ) = a 0 T ( C V ) + n ---
2
16 4.612 1.570 18.85 .3925 3 j j j
j=1
18 6.389 2.213 29.81 .5573 (1)
20 8.434 2.990 44.61 .7601
25 14.39 5.494 101.3 1.443 ∫ + a 4 E ( θ E /T ) + a 5 K ( θ L /T , θ U /T ) ,
30 20.96 8.693 189.5 2.375
35 27.64 12.43 311.0 3.539 where n is the number of atoms in the molecule (n = 7
for K2MoO4); D and E are the Debye and Einstein func-
40 34.17 16.54 465.7 4.903
tions; K is the Kieffer function [16]; θ1, θ2, θ3, θE, θL,
45 40.42 20.93 652.3 6.438 and θU are the characteristic temperatures (157, 309,
50 46.34 25.50 869.4 8.115 1546, 605, 230, and 469 K, respectively); and a0, a1, a2,
60 57.08 34.92 1388 11.79 a3, a4, and a5 are linear coefficients (1.1043 × 10–7 mol/J,
70 66.42 44.44 2006 15.78 0.8757, 0.8429, 0.7143, 0.1071, and 0.1143, respec-
80 74.49 53.85 2712 19.95
tively). The a0, …, a5 and θ1, …, θU values were deter-
mined by the nonlinear least squares method. The pro-
90 81.52 63.04 3493 24.23 cedure for calculations was described in detail in [17].
100 87.68 71.95 4339 28.56 Equation (1) was used to calculate the heat capacity,
110 93.13 80.57 5244 32.90 entropy, reduced Gibbs energy, and enthalpy of potas-
120 97.99 88.89 6200 37.22 sium molybdate over the temperature range 0–330 K
(Table 3),
130 102.4 96.90 7202 41.50
140 106.3 104.6 8246 45.74 C °p (298.15 ä) = 143.1 ± 0.2 J/(mol K),
150 109.9 112.1 9327 49.92 S°(298.15 ä) = 199.3 ± 0.4 J/(mol K),
160 113.3 119.3 10440 54.03 H°(298.15ä)–H°(0) = 28.41 ± 0.03 kJ/mol,
170 116.3 126.3 11590 58.07 Φ°(298.15 ä) = 104.0 ± 0.4 J/(mol K).
180 119.2 133.0 12770 62.05 The errors specified were estimated according
190 121.9 139.5 13980 65.96 to [18].
200 124.4 145.8 15210 69.80 Equation (1) was used to extrapolate the C °p (T)
210 126.8 151.9 16460 73.56 dependence to the temperature of the first phase transi-
tion (600 K). The heat capacity, entropy, and enthalpy
220 129.0 157.9 17740 77.26
of ä2åÓO4 calculated this way are listed in Table 4.
230 131.1 163.7 19040 80.89 The substantial difference between the heat capacities
240 133.1 169.3 20360 84.46 of sodium [11] and potassium (Fig. 1) molybdates is
250 135.0 174.8 21700 87.96 likely related to the difference between their structures
and the masses of the alkali metals.
260 136.9 180.1 23060 91.40
The S°(K2MoO4, cr, 298.15 K) value obtained in this
270 138.6 185.3 24440 94.78 work was used to calculate the Gibbs energy of forma-
280 140.3 190.4 25840 98.11 tion of potassium molybdate from the elements. We
290 141.8 195.3 27250 101.4 used the mean (according to [19, 20]) enthalpy of for-
mation ∆fH°(K2MoO4, cr, 298.15 K), –1498.46 ±
298.15 143.1 199.3 28410 104.0 1.00 kJ/mol. The entropies of the elements necessary
300 143.3 200.2 28670 104.6 for the calculations were taken from handbook [21]
310 144.8 204.9 30110 107.7 (J/(mol K)): S°(K, cr, 298.15 K) = 64.68 ± 0.20, S°(Mo,
cr, 298.15 K) = 28.57 ± 0.20, and S°(O2, g, 298.15 K) =
320 146.2 209.5 31570 110.9
205.035 ± 0.020. As a result, we obtained the stan-
330 147.5 214.0 33040 113.9 dard Gibbs energy of formation of potassium molyb-

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 3 2009

 A CALORIMETRIC STUDY OF THE THERMODYNAMIC PROPERTIES 331

date from the elements ∆fG°(K2MoO4, cr, 298.15 K) = Table 4. Calculated thermodynamic functions of K2MoO4
–1388.52 ± 1.80 kJ/mol. over the temperature range 340–600 K (∆H° in J/mol and the
All the heating curves of K2MoO4 samples (mass no other functions in J/(mol K))
more than 0.030 g) contained endothermic effects T, K C °p (T) S°(T) H°(T)–H°(0) Φ°(T)
(accordingly, cooling curves contained exothermic
effects) related to reversible phase transitions known 340 148.74 218.45 34517.6 116.93
from the literature (Table 5). The thermal effect values 360 151.10 227.02 37516.4 122.81
were determined using standard programs by the 380 153.26 235.25 40560.3 128.51
graphic integration of differential scanning calorimetry
curve peaks. Errors in integration were of 0.2 to 6% 400 155.23 243.16 43645.6 134.05
depending on the shape and intensity of the peaks. The 420 157.04 250.78 46768.6 139.43
temperatures of transitions were found from the inter- 440 158.70 258.12 49926.3 144.65
section of the tangent to the forefront of the peak with 460 160.23 265.21 53115.7 149.74
the base line of the differential scanning calorimetry
curve (TÂ) and from the temperature corresponding to 480 161.63 272.06 56334.5 154.70
the peak maximum (T). In conformity with the usual 500 162.93 278.69 59580.3 159.53
practice, we assumed that TÂ corresponded to the tran- 520 164.13 285.10 62851.0 164.23
sition temperature Ttr. 540 165.24 291.31 66144.8 168.82
The enthalpies of potassium molybdate phase tran- 560 166.26 297.34 69459.9 173.30
sitions measured by differential scanning calorimetry
are presented in Table 6 and Fig. 2 (for convenience of 580 167.21 303.19 72794.6 177.68
calculations, all the values in Tables 5 and 6 are given 600 168.10 308.88 76147.8 181.97
with excess significant digits). Note that our data on the
kIV kIII and kIII kII transitions poorly agree
with those reported in [3] and obtained by heating obtained on the SETARAM calorimeter at heating
potassium molybdate in a sealed container in air at a rates of 5 and 10 K/min coincided (the mean of two
rate of 0.5 K/min. When comparing our data with [2], it measurements was 12.55 ± 0.34 kJ/mol) but were
must be borne in mind that the error in heat effect mea- higher by 10% than the values cited in [2]. The
surements performed in [2] is no less than 6%. As can enthalpy ∆trH(kIV kIII) was taken to equal the
be seen from Table 6, the enthalpies of reverse transi- mean of three measurements, 11.34 ± 1.62 kJ/mol. The
tions (–∆trH(exo)) are usually larger than ∆trH(endo). temperature of the transition (596 ± 1 K) was obtained
The same was noticed in [3] for the transition at 730 K. as the mean of two measurements performed at a heat-
ing rate of 5 K/min.
The kIV(monocl.) kIII(rhomb.) Transition The cooling curves recorded immediately after heat-
ing the samples above the melting point did not contain
The enthalpy of the transition ∆trH(endo) obtained the effect corresponding to the reverse kIII kIV
using the METTLER calorimeter was higher than that transition. This circumstance related to a substantial
reported in [3] by 7.5%. The enthalpies ∆trH(endo) hysteresis of the transition to the monoclinic phase has

Q, mW
Cp, J/(mol K) 160 ÖıÓ kI ← l
160
2 120

120 80
1
40 kIII ← kII Cooling
80
0 Heating
40
–40 kIV → kIII kIII → kII

kI → l
–80
0 50 100 150 200 250 300 400 600 800 1000 1200 1400
T, K T, K

Fig. 1. Temperature dependences of the heat capacities of Fig. 2. Heating–cooling cycle for potassium molybdate
(1) Na2MoO4 and (2) K2MoO4. recorded at a rate of 10 K/min; Q is the heat flux.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 3 2009

332 GAVRICHEV et al.

Table 5. Literature data on the enthalpies of K2MoO4 phase with different weights at different heating rates closely
transitions (kJ/mol) agree with each other. The enthalpy of the transition,
∆trH(kIII kII), is 1.04 ± 0.06 kJ/mol (the mean of
Transition Ttr , K ∆H Refs.
three measurements). Accordingly, –∆trH(kII kIII) =
kIV(monocl.) 589 ± 10 9.79 ± 1.25 [1] 1.70 ± 0.03 kJ/mol (the mean of two measurements).
kIII(rhomb.) 569 ± 2 11.34 [2] Interestingly, TÂ(exo) and TÂ(endo) coincide for differ-
556 8.27 ± 0.10 [3] ent samples. The conclusion can be drawn that this tran-
sition is not accompanied by hysteresis.
kIII(rhomb.) 723 ± 5 0.84 ± 0.21 [1]
kII(hex.) 725 ± 2 1.13 [2]
730 0.64 ± 0.03 [3] The kII(hex.) kI(hex.) Transition
kII(hex.) kI(hex.) 749 ± 10 – [1]
The kII kI transition was only observed when
kI(hex.) l 1199 ± 1 38.70 ± 2.09 [1] the heating curve was recorded on the METTLER cal-
1199 ± 2 38.70 [2] orimeter; this transition had a vanishingly small ∆trH
1201 ± 2 34.70 ± 0.7 [4] value, as was also mentioned earlier. This can be
Note: In Handbook [1], the enthalpies of transitions are given tak- explained by the occurrence of the transition from the
ing the values from [2, 3] into account. modulated hexagonal phase of kII to the hexagonal
phase of kI with an insignificant monotonic increase in
cell parameters, which experience a small jump at
Table 6. Thermal effects on potassium molybdate DSC 753 K, that is, without a change of the structural type
curves (kJ/mol) of the lattice (as is seen from [9]).
v Phase transition Te , K Tp , K ∆H
Heating (endothermic effects) The kI(hex.) l Transition
5* kIV kIII 594.9 606.5 8.91
The TÂ(kI l) temperature is 1203.6 ± 0.6 K,
5 596.4 611.6 12.53 ± 0.17
which is higher by ~5 K than the literature values
10 610.3 627.2 12.57 ± 0.15 (Table 5). The enthalpy of melting ∆mH = 40.14 ±
5* kIII kII 726.5 729.2 1.02 1.25 kJ/mol is larger by 4% compared with [2] and by
5 728.0 732.3 1.10 ± 0.01 16% compared with the mixing microcalorimetry data
10 724.5 733.2 1.01 ± 0.02 [4]. The enthalpy of crystallization, 42.59 ± 1.54 kJ/mol,
is larger than the enthalpy of melting by 5% on average.
5* kII kI 752.8 755.6 0.024
5 kI l 1204.2 1209.3 41.28 ± 0.04 The enthalpies (kJ/mol) of phase transitions largely
obtained using the DSC 2000 K high-temperature iner-
10 1203.0 1211.7 39.01 ± 0.07
tial calorimeter are:
Cooling (exothermic effects)
5 kII kIII 725.9 721.2 –1.69 ± 0.01 ∆trH(kIV kIII) = 11.34 ± 1.62 (Ttr = 596 ± 1 ä),
10 726.2 721.7 –1.71 ± 0.01
5 l kI 1197.2 1191.9 –43.24 ± 0.17 ∆trH(kIII kII) = 1.04 ± 0.06 (Ttr = 726 ± 2 ä),
10 1181.5 1178.9 –41.93 ± 0.71
∆trH(kII kI) = 0.024 (Ttr = 753 ä),
* Data obtained on the METTLER TA 4000 unit, the other data
were obtained on SETARAM DSC 2000 K; v is the heating/cool-
ing rate, k/min ∆mH(kI l) = 40.14 ± 1.25 (Tm = 1204 ± 1 ä).

been discussed in detail (e.g., see [3, 9]). As in [3], the
cooling curve recorded on the METTLER calorimeter
contained a saw-tooth peak at almost the same temper-
ature, 434–380 K. This peak was most likely related to
the beginning of the kIII kIV transition.
The kIII(rhomb.) kII(hex.) Transition
As mentioned, phase III has a modulated orthorhom-
bic structure [9, 10], and phase II, a modulated hexago-
nal structure [9]. Our DSC data obtained for samples
CONCLUSIONS
To summarize, a detailed study of the heat capacity
of potassium molybdate was performed to obtain the
temperature dependences of the thermodynamic func-
tions in the region of low temperatures. The experimen-
tal data were used to refine the S°(298.15 ä) and
∆fG°(298.15 ä) values for potassium molybdate. The
parameters of potassium molybdate phase transitions
were determined by differential scanning calorimetry.
The DSC data were well reproducible as concerns both
temperatures and enthalpies of thermal effects.

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 A CALORIMETRIC STUDY OF THE THERMODYNAMIC PROPERTIES
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