J. Chem.

Thermodynamics 70 (2014) 3945

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Gibbs free energy of formation of rhodium suldes

K.T. Jacob , Preeti Gupta
Department of Materials Engineering, Indian Institute of Science, Bangalore 560012, India

a r t i c l e

i n f o

a b s t r a c t
Using a solid-state electrochemical technique, thermodynamic properties of three sulde phases (RhS0.882, Rh3S4, Rh2S3) in the binary system (Rh + S) are measured as a function of temperature over the range from (925 to 1275) K. Single crystal CaF2 is used as the electrolyte. The auxiliary electrode consisting of (CaS + CaF2) is designed in such a way that the sulfur chemical potential converts into an equivalent uorine potential at each electrode. The sulfur potentials at the measuring electrodes are established by the mixtures of (Rh + RhS0.882), (RhS0.882 + Rh3S4) and (Rh3S4 + Rh2S3) respectively. A gas mixture (H2 + H2S + Ar) of known composition xes the sulfur potential at the reference electrode. A novel cell design with physical separation of rhodium suldes in the measuring electrode from CaS in the auxiliary electrode is used to prevent interaction between the two sulde phases. They equilibrate only via the gas phase in a hermetically sealed reference enclosure. Standard Gibbs energy changes for the following reactions are calculated from the electromotive force of three cells: 2.2667Rh (s) + S2 (g) ? 2.2667RhS0.882 (s),

Article history: Received 12 September 2013 Accepted 9 October 2013 Available online 17 October 2013 Keywords: Sulfur potential System (Rh + S) Emf measurement Gibbs energy of formation

Dr Go 2330=J mol 288690 146:18 T =K ;

4.44RhS0.882 (s) + S2 (g) ? 1.48Rh3S4 (s),

Dr Go 2245=J mol 245596 164:31 T =K;
1

4Rh3S4 (s) + S2 (g) ? 6Rh2S3 (s),

Dr Go 2490=J mol 230957 160:03 T =K:
Standard entropy and enthalpy of formation of rhodium suldes from elements in their normal standard states at T = 298.15 K are evaluated. 2013 Elsevier Ltd. All rights reserved.
1

1. Introduction Processing ore concentrates containing platinum group metals (PGM) involves smelting to produce a (Fe + Co + Ni + Cu) matte that acts as PGM collector [1]. Hence, accurate information of precious metalsulfur systems is useful for optimizing PGM recovery. In recent years RhxSy, a balanced mixture of (Rh2S3 + Rh3S4 + Rh17S15) with Rh3S4 as an active phase, has emerged as a promising electro-catalyst for the reduction of molecular oxygen to water in acidic medium [28]. It is the only commercial chalcogenide electro-catalyst available for oxygen reduction reaction (ORR) applications, such as depolarized electrolysis of HCl. The catalyst has potential applications in fuel cells, especially direct methanol fuel cells (DFMCs). Accurate thermodynamic data for rhodium suldes

Corresponding author. Tel.: +91 80 2293 2494; fax: +91 80 2360 0472.
E-mail (K.T. Jacob). addresses: katob@materials.iisc.ernet.in, ktjacob@hotmail.com

will enable better characterization of the electrochemical processes. In the (Rh + S) binary system, four solid phases, Rh17S15 (RhS0.882), Rh3S4, Rh2S3 and RhS3 are reported [9], but the phase diagram is incomplete. The diagram in the compilation of Massalski et al. [9] indicates the decomposition of Rh17S15 to a Rhrich liquid sulde (matte) and sulfurrich gas at T  1373 K. Taylor [10] measured the liquidus and phase transformation temperatures of 11 samples covering the composition range from (45 to 67) atom percent Rh by employing differential thermal analysis (DTA). Contrary to the earlier phase diagram [9], the results of Taylor [10] show the existence of three-phase equilibrium consisting of Rh17S15, Rh3S4 and (Rh + S) liquid solution at T = 1386 K. Rh3S4 decomposes at T = 1403 K to form Rh2S3 and (Rh + S) liquid. The decomposition temperature of Rh2S3 was not determined. Crystallographic studies on Rh17S15 (RhS0.882) were reported by Geller [11,12]. Rh17S15 is iso-structural with Pd17Se15 and has cubic structure with space group Pm3m and two formula units per unit

0021-9614/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jct.2013.10.011

40

K.T. Jacob, P. Gupta / J. Chem. Thermodynamics 70 (2014) 3945

cell [11,12]. Rh17S15 is a naturally occurring mineral known as miassite and was rst synthesized by Matthias et al. [13]. Naren et al. [14] have conrmed crystallographic data for Rh17S15 and found superconductivity below T = 5.4 K caused by the presence of high density of states of Rh d bands near Fermi level. The second sulde, Rh3S4, commonly known as kingstonite, crystallizes with monoclinic structure in the space group C2/m [15]. Rh2S3, often referred to bowieite, has orthorhombic crystal structure with space group Pbcn [16]. The Gibbs energy of formation of rhodium suldes above T = 1084 K has been measured using different techniques [10,17,18]. Taylor [10] used the Knudsen effusion technique for measuring the sulfur pressures within the temperature range from (1213 to 1363) K. Larson and Elliott [17] employed a solid-state cell with stabilized-zirconia as the electrolyte, pure oxygen as the reference electrode and mixture of Rh and RhxS under 101.3 kPa pressure of SO2 gas as the measuring electrode in the temperature range from (1084 to 1357) K. They were unable to identify the sulde phase in equilibrium with Rh. According to the phase diagram suggested by Taylor [10], metallic Rh coexists with liquid (Rh + S) solution (matte) above T = 1213 K. There is a signicant difference in the temperature dependence of the Gibbs energy of formation of the metal saturated phase, Rh17S15 (RhS0.882) reported by Taylor [10] and RhxS reported by Larson and Elliott [17]. Juza et al. [18] used the manometric technique to measure the dissociation pressure two rhodium suldes (Rh3S4 and Rh2S3) within the temperature range from (1226 to 1356) K. A solid-state electrochemical cell based on single crystal CaF2 as the electrolyte is used in this study to extend the measurements to lower temperature so that thermodynamic properties are better dened.

sealed in evacuated ampoules. The mixture is reacted initially at T = 673 K for 48 h. Temperature is then raised slowly. The nal reaction temperatures are T = 1200 K for Rh17S15 (RhS0.882) and T = 1373 K for Rh3S4 and Rh2S3. After holding at the highest temperature for 72 h, the ampoules are furnace cooled. Sulfur condensation on the ampoule indicates incomplete reaction. In such cases, additional heat treatment was done till all the sulfur is consumed. Formation of single phase suldes is conrmed by X-ray diffraction (XRD) and their composition veried by energy dispersive spectroscopy (EDS). The lattice parameters of the synthesized compounds are a = 0.9913 nm for Rh17S15, a = 1.031 nm, b = 1.069 nm, c = 0.6210 nm for Rh3S4 and a = 0.8464 nm, b = 0.5987 nm, c = 0.6141 nm for Rh2S3. 2.2. Electrochemical measurements The electromotive force (e.m.f.) of the following solid-state electrochemical cells were measured,

Au;H2 H2 S=CaS CaF2 ==CaF2 ==CaF2 CaS=Rh RhS0:882 ; Au ; Au;H2 H2 S=CaS CaF2 ==CaF2 ==CaF2 CaS=RhS0:882 Rh3 S4 ; Au; Au;H2 H2 S= CaS CaF2 ==CaF2 == CaF2 CaS=Rh3 S4 Rh2 S3 ; Au: III II I

2. Experimental procedure 2.1. Materials Purity and sources of the chemicals used in this study are given in table 1. Optical grade single crystals of CaF2 in the form of disks of 1.5 cm in diameter and 0.2 cm thick, were obtained from Harshaw Chemical Company. A high-purity gas mixture of (H2 + H2S + Ar) of constant composition containing 0.8 volume fraction Ar, 0.16654 volume fraction hydrogen and 0.03346 volume fraction H2S supplied by Matheson is used to dene the sulfur partial pressure at the reference electrode. The high concentration of Ar in the gas mixture minimizes thermal segregation in the gas mixture caused by the large difference in the atomic mass of the constituents H2 and H2S. Three rhodium suldes Rh17S15 (RhS0.882), Rh3S4 and Rh2S3 are prepared by direct reaction between Rh and S in evacuated and sealed silica ampoules at high temperatures. Rh powder is rst reduced under H2 gas at T = 873 K to remove surface oxide. Powders of Rh and S are mixed in the appropriate stoichiometric ratio and

Single crystal CaF2 used as the solid electrolyte is an F ion conductor and responds to the difference in the chemical potential of uorine at the two electrodes. At each electrode, (CaS + CaF2) pellet is used to convert the sulphur chemical potential into an equivalent uorine potential [19] by virtue of the exchange reaction;

CaF2 1=2S2 ! CaS F2 :

TABLE 1 Sources and purity of chemicals used in the experiment. Chemicals Rh (powder) CaF2 (single crystal) CaF2 (powder) CaS Au wire (H2 + H2S + Ar) gas mixture S (powder) Sources Alfa aesar Harshaw chemicals Apache chemical company Ventron corporation Johnson matthey and mallory ltd. Matheson Alfa aesar Mass fraction purity 0.9995 0.9999 0.99999 0.9999 0.999 0.99999 0.995

There is negligible solid solubility between CaF2 and CaS and both phases are present at unit activity at the auxiliary electrodes. The cell e.m.f. is thus related to the difference in the sulfur chemical potential established at the electrodes. Several examples of the use of auxiliary electrodes are reported in the literature. Auxiliary electrode of CaS has been used to convert sulfur chemical to an equivalent oxygen potential in conjunction with CaO-stabilized ZrO2 [20]. An auxiliary electrode of Na2S has been used for sulfur potential measurement along with Na b-alumina, which is a Na+ ion conductor [21]. Na2SO4 has been used as an auxiliary electrode in probes for SO2/SO3 based on Na b-alumina [22]. Similarly, a (CaSO4 + CaF2) auxiliary electrode has been used to measure the partial pressure of SO3 using a solid-state cell based on CaF2 as electrolyte [23]. The gas reference electrode on the left-hand side of each cell is connected to the negative terminal of a high impedance (>1012 ) digital voltmeter. The (H2 + H2S + Ar) gas mixture establishes the sulfur potential at the reference electrode. A mixture of two adjacent phases in the (Rh + S) system xes the sulfur potential at the measuring electrodes. When the sulfur chemical potential of the measuring electrode is higher than that of the reference, the cell e.m.f. is positive. The e.m.f. values for cell (I) is measured in the range temperature from (925 to 1200) K, cell (II) and cell (III) from (925 to 1275) K. The upper temperature limit for cell (I) is set by the formation of eutectic liquid at T = 1213 K [11]. The upper limit for cells (II) and (III) is set by the softening of CaF2 single crystal, which serves as an electrolyte. A schematic outline of apparatus used for e.m.f. measurement is displayed in gure 1. Auxiliary electrode pellets composed of (CaS + CaF2) are spring-loaded on both sides of single crystal CaF2

K.T. Jacob, P. Gupta / J. Chem. Thermodynamics 70 (2014) 3945

41

using a system of alumina rods and slabs, with a gauze made of Au sandwiched between the electrolyte and each auxiliary electrode. The electrolyte and electrode pellets are stacked vertically. Gold electrical leads are spotwelded to the gauze on either side of the electrolyte. An alumina crucible containing equimolar mixtures of (Rh + RhS0.882), (RhS0.882 + Rh3S4) or (Rh3S4 + Rh2S3) is placed over the top auxiliary electrode supported on a short silica tube. This alumina crucible with V-shaped notches cut at the top, is covered by a second inverted alumina crucible, edges of which are ground to form a knife edge. When spring loaded against the CaF2 single crystal at high temperatures, the knife edge cuts into the single crystal making a gas-tight joint. The electric lead to the auxiliary electrode adjacent to the measuring electrode passes through a small orice in the inverted alumina crucible. The orice is closed with a glass seal. Thus the measuring electrode is isolated. The sulfur partial pressure generated by the decomposition of rhodium sulde in the alumina crucible is transmitted to the auxiliary electrode inside the enclosure via the gas phase. The physical separation of the auxiliary electrode and rhodium suldes on the measuring side is designed to prevent interaction between calcium and rhodium suldes. The interaction is via the gas phase. A constant sulfur partial pressure is established inside the inverted alumina crucible The cell assembly is mounted inside a vertical alumina tube. The ends of the tube are closed with brass caps, which have provision for electrical leads and gas inlet and outlet. The alumina tube enclosing the cell is evacuated and relled with the (H2 + H2S + Ar) gas mixture three times. The gas mixture with controlled (pH2 S =pH2 ) ratio xes the sulfur potential at reference electrode. Initially when the cell is cold and the knife edge has not formed a hermetic seal around the reference electrode, the gas mixture also enters the reference enclosure. However, when the cell is heated to T = 1200 K, the knife edge of the inverted alumina crucible penetrates the CaF2 single crystal to make a hermetic seal. The limited quantity

of H2S and H2 thus trapped inside the inverted alumina crucible interacts with the rhodium suldes to establish a unique sulfur potential and H2S/H2 ratio inside the reference enclosure at constant temperature. The outer alumina tube enclosing the cell is suspended in a vertical resistance furnace such that the cell is situated in the constant temperature zone (1 K). An earthed Kanthal shield is placed between the vertical alumina tube and the furnace to avoid the induced e.m.f. on cell leads from the furnace winding. The assembled cell is rst heated to T = 1200 K to from the hermetic enclosure around the reference electrode. The e.m.f. is then monitored as a function of time at different temperatures. The temperature of the cell is measured with a Pt/Pt-13%Rh thermocouple checked against the melting point of Au. The temperature is controlled to (1 K). The e.m.f. of the cell becomes steady in 6 h at T = 1200 K. To check the reversibility of the cells, a small current (15 lA) is passed through the cell in each direction for 10 min using an external D.C. source. The e.m.f. is then observed as a function of time. It is veried that the e.m.f. returned to the same value after successive micro-coulometric titrations in opposite directions, thus conrming electrochemical reversibility. The e.m.f. is found to be reproducible when the temperature is approached from higher and lower sides, conrming thermal reversibility. Changing the ow rate of the reference gas mixture in the range from (150 to 300) ml min1 did not affect the e.m.f. After the completion of each experiment, the cell is cooled and the electrodes are checked by optical and scanning electron microscopy and X-ray diffraction. No signicant change in the phase composition of the electrodes during electrochemical measurement is observed. 3. Results and discussion The measured e.m.f.s of the three cells are listed in table 2 and displayed in gure 2. They show linear variation with temperature. In the temperature range of measurement, the e.m.f. of cell (I) is negative, while the e.m.f. of the other two cells are positive. Expressions obtained from least-squares regression analysis are:

EI 3:58=mV 278:84 0:1902 T =K; EII 3:18=mV 167:18 0:2372 T =K; EIII 4:22=mV 129:25 0:2261 T =K:

2 3 4

The uncertainty limits correspond to twice the standard deviation. The gas mixture (H2 + H2S + Ar) of known composition establishes
Table 2 Reversible e.m.f. (E) of the solid-state electrochemical cells (I)(III) at different temperatures (T). Cell I T/K 925 975 1000 1065 1125 1150 1200 E/mV 100.5 1.7 95.2 1.5 89.6 1.5 76.1 1.4 66.6 1.3 58.5 1.3 50 1.2 Cell II T/K 925 975 1025 1075 1124 1150 1175 1228 1275 E/mV 50.8 1.5 64.4 1.4 76.7 1.4 89.7 1.4 96.7 1.3 106.8 1.3 112.4 1.3 124.5 1.3 134 1.2 Cell III T/K 925 937.5 959 1024 1028.5 1075 1125 1173 1197 1215 1230 1259 1275 E/mV 80 2 85 2 85.5 1.9 104 1.9 101 1.9 114 1.8 125 1.8 138 1.8 137 1.8 146 1.7 150 1.7 154 1.7 161.1 1.7

FIGURE 1. A line sketch of the solid-state electrochemical cell assembly used for this study.

42

K.T. Jacob, P. Gupta / J. Chem. Thermodynamics 70 (2014) 3945

2:2667Rh s S2 g ! 2:2667RhS0:882 s; 4:44RhS0:882 s S2 g ! 1:48Rh3 S4 s; 4Rh3 S4 s S2 g ! 6Rh2 S3 s:

15 16 17

The standard Gibbs energy change for the reactions (15)(17) are evaluated by combining standard Gibbs energy change for the cell reactions (12)(14) with standard Gibbs energy of formation for H2S (gas) from the NISTJANAF tables [24] represented by equation (6). Thus,

Dr15 Go 2330=J mol 288690 146:18 T =K; Dr16 Go 2245=J mol 245596 164:31 T =K; Dr17 Go 2490=J mol 230957 160:03 T =K:
1 1

18 19 20

FIGURE 2. Temperature dependence of the e.m.f. of the solid-state electrochemical cells: d (orange online), cell (I); N (blue online), cell (II); (magenta online), cell (III). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

the sulfur partial pressure over the (CaS + CaF2) electrode on the reference side by virtue of the reaction:

2H2 g S2 g ! 2H2 S g:

The standard Gibbs energy of formation of H2S from NIST-JANAF [24] tables over the temperature range from (900 to 1300) K can be represented by the equation:

Dr5 Go 1880=J mol 181074 99:46 T =K:

For cell (I), the virtual cell reaction is:

2:2667RhS0:882 s 2H2 g ! 2:2667Rh s 2H2 S g:

Similarly, for cells (II) and (III) the net cell reactions can be written as:

1:48Rh3 S4 s 2H2 g ! 4:44RhS0:882 s 2H2 S g; 6Rh2 S3 s 2H2 g ! 4Rh3 S4 s 2H2 S g:

8 9

Standard Gibbs energy change for the reactions (15)(17) are plotted as a function of temperature and compared with prior measurements reported in the literature in gures 3, 4 and 5, respectively. For the formation of solid RhS0.882 according to reaction (15), the standard Gibbs energy change obtained directly in this study at lower temperatures is in good agreement with data reported by Taylor [10] at higher temperatures, as shown in gure 3. Taylor [10] used the Knudsen effusion technique to measure the sulfur partial pressure. Since a liquid phase of variable composition separates solid Rh and RhS0.882 phases above T = 1213 K, Taylor [10] had to measure sulfur pressure as a function of composition of the liquid phase at different temperatures, integrate GibbsDuhem equation to obtain the activity of Rh as a function of composition and then compute Gibbs energy of formation of RhS0.882. Considering the procedure involved, the agreement between the two sets of data is encouraging. It is to be noted that the standard Gibbs energy change for reaction (15) is equal to the chemical potential of sulfur for (Rh + RhS0.882) equilibrium. Also shown in gure 3, are the chemical potentials corresponding to (Rh + liquid) equilibrium reported by Taylor [10], and (Rh + RhxS) equilibrium reported by Larson and Elliott [17] using a cell and with stabilized-zirconia

Gibbs energy changes for the reactions (7)(9) can be computed from the e.m.f. using relation:

DG gFE;

10

where g = 4 is number of electrons involved in the electrode reactions, F = 96485 J V1 is the Faraday constant and E/V is the e.m.f. measured. The standard Gibbs energy change for the cell reactions (7)(9), can be computed from the e.m.f. and H2S/H2 ratio in the gas mixture owing over the reference electrode:

DGo DG 2RT lnpH2 =pH2 S gFE 2RT lnpH2 S =pH2 ;

11

where R = 8.3144 J K1 mol1 is the gas constant and ratio of partial pressures of H2S to H2 in the reference gas mixture is (pH2 S =pH2 ) = 0.2009. Employing equation (11), the standard Gibbs energy change for the cell reactions (7)(9) are obtained as:

Dr7 Go 1382=J mol 107616 46:72 T =K; Dr8 Go 1227=J mol 64522 64:85 T =K; Dr9 Go 1636=J mol 49883 60:57 T =K:
1 1

12 13 14
FIGURE 3. Standard Gibbs energy change for the reaction 2.2667Rh (s) + S2 (g) ? 2.2667 RhS0.882 (s) as a function of temperature: (black online), this study; N (green online), Taylor [10]; (red online), RT ln P S2 in the twophase (Rh + liquid) [10]; (blue online), standard Gibbs energy change for the reaction xRh (s) + S2 (g) ? RhxS (s) [17]. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

The sulfur chemical potential dening reactions occurring at the measuring electrodes of the cells (I)(III) are:

K.T. Jacob, P. Gupta / J. Chem. Thermodynamics 70 (2014) 3945

43

Employing a manometric technique, Juza et al. [18] measured the decomposition pressures of Rh3S4 and Rh2S3 in the temperature range from (1226 to 1356) K. Their data are compared with the results of this study in gures 4 and 5, respectively. There is good agreement, although temperature dependence of Gibbs energy change shows some difference. In view of difculties in accurate calibration of differential Bourdon-type gauge at moderately high temperatures required to prevent condensation of sulfur vapor, the results of this study are considered to be superior providing more accurate thermodynamic information. Molar thermodynamic properties for three rhodium suldes can be computed using the results presented above:

Rh s 0:441S2 g ! RhS0:882 s;

21

Df Go RhS0:882 1030=J mol

127361 64:49 T =K; 3Rh s 2S2 g ! Rh3 S4 s;
FIGURE 4. Standard Gibbs energy change for the reaction 4.44RhS0.882 (s) + S2 (g) ? 1.48 Rh3S4 (s) as a function of temperature: (black online), this study; d (red online), Juza et al. [18]. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

22 23 24 25 26

Df Go Rh3 S4 3445=J mol 548026 304:5 T =K;

2Rh s 1:5S2 g ! Rh2 S3 s;

Df Go Rh2 S3 2335=J mol 403844 229:67 T =K:

In equations (22), (24), and (26), the temperature-independent term gives the enthalpy of formation (Df Ho T av ) at an average temperature of experiment and the temperature-dependent term with reversed sign gives the corresponding entropy change (Df So T av ). The average temperature for reaction (21) is Tav = 1063 K and for reactions (23) and (25) Tav = 1100 K. To evaluate thermodynamic properties of three rhodium suldes at T = 298.15 K heat capacity of reactants and products as a function of temperature is required. Since heat capacity of rhodium suldes has not been measured, an average value for the change in heat capacity suggested by Kubaschewski and Alcock [25] may be used. The change in heat capacity (DCP) for reactions involving a gas phase such as:

A s bS2 g ! AS2b s; aAx Sy s bS2 g ! Aax Say2b s;

can be approximated as:
FIGURE 5. Standard Gibbs energy change for the reaction 4Rh3S4 (s) + S2 (g) ? 6Rh2S3 (s) as a function of temperature: (black online), this study; d (red online), Juza et al. [18]. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

27 28

DC P =J K1 mol

12:552b:

29

as the electrolyte in the temperature ranges from (1084 to 1357) K. Larson and Elliott [17] were unable to identify the sulde phase formed in their experiments since XRD data for the sulde did not match structure information in the literature [13,18]. In the higher temperature reaches of their experiment, a liquid phase is expected to coexist with Rh according to the phase diagram of Taylor [10]. Their reported sulfur potentials match well with that of Taylor [10] for (Rh + liquid) equilibrium. Since the results of Larson and Elliott [17] do not show a change of slope at the eutectic temperature, they probably encountered super-cooled liquid below T = 1213 K. DTA analysis by Taylor [10] of a liquid (Rh + S) sample during cooling indicated suppression of the eutectic reaction by T = 180 K. This would indicate that the measurements of Larson and Elliott [17] correspond to (Rh + liquid) equilibrium in whole range of temperature. The composition of the liquid would vary with temperature, dened by the liquidus curve and its extension below the eutectic.

Thus the calculated average values for DCP for reactions (21), (23), and (25) are 5.534, 25.106 and 18.829 J K1 mol1, respectively. The standard entropy and enthalpy of formation for three rhodium suldes according to reactions (21), (23), and (25) at T = 298.15 K can be calculated using the relations:
o Df So 298:15K Df ST av

T av

DC P =T dT 30

298:15 K

Df So T av DC P ln T av ln 298:15;
o Df H o 298:15 K Df H T av

T av

DC P d T
31

298:15 K

Df H o T av DC P T av 298:15:
Df So 298:15 K

Values of for RhS0.882, Rh3S4, Rh2S3 corresponding to reactions (21), (23), and (25) are (71.53 3.45), (337.27 11.42) and (254.25 7.68) J K1 mol1, respectively. Standard entropy (So of rhodium suldes at 298:15 K ) T = 298.15 K can be calculated by combining the standard entropy change for the reactions (21), (23), and (25) at T = 298.15 K derived

44

K.T. Jacob, P. Gupta / J. Chem. Thermodynamics 70 (2014) 3945

from equation (30) and standard entropies of elements of Rh (31.56 0.21) J K1 mol1 and S2 (g) (228.1 0.42) J K1 mol1 from the thermodynamic data compilation of Pankratz [26]. Thus, So 298:15K for RhS0.882, Rh3S4 and Rh2S3 are (60.62 3.46), (213.61 11.47) and (151.02 7.71) J K1 mol1, respectively. The values of Df Ho 298:15 K calculated using equation (31) corresponding to reactions (21), (23), and (25), where the standard state for sulfur is diatomic gas, are (131.6 3.8), (568.2 12.3) and (418.9 8.3) kJ mol1, respectively. Since the standard state for sulfur at T = 298.15 K is solid sulfur with orthorhombic structure, the enthalpy for the change of standard state of sulfur from diatomic gas to solid sulfur needs to be considered. Pankratz [26] gives for the reaction, 2S (ortho) ? S2 (g), Dr Ho 298:15K 1 0:9=kJ mol 128:5: Thus, the standard enthalpy of formation of rhodium suldes from solid Rh and solid orthorhombic sulfur 1 are Df Ho for RhS0.882, Df Ho 298:15K = (74.93 3.9) kJ mol 298:15K = 1 (311.2 12.4) kJ mol for Rh3S4 and Df Ho 298:15K = (226.2 8.4) kJ mol1 for Rh2S3. Figure 6 shows the Gibbs energy of mixing (DmixG) at T = 1100 K and enthalpy of mixing at T = 298.15 K as a function of composition for the system (Rh + S); the standard state of rhodium is solid metal and sulfur is diatomic gas. The values for three rhodium suldes are calculated by dividing the Gibbs energy of formation from equation (22), (24), and (26) by the total number of atoms of rhodium and sulfur present in each rhodium sulde. The minimum for both Gibbs energy and enthalpy of mixing occurs at the composition corresponding to Rh2S3. The enthalpy of solid sulfur relative to diatomic gas is also shown in the diagram. The length of the arrows in the gure is a measure of the enthalpy of mixing (DmixH) with respect to solid rhodium and solid sulfur. Recently, Diguez and Marzari [27] have performed rst-principles calculations of structural, electronic and thermodynamic properties of the three rhodium suldes using density-functional theory (DFT) in the Kohn-Sham framework. They have reported cohesive energies and derived enthalpies of formation of Rh17S15 (RhS0.882), Rh3S4 and Rh2S3. Unfortunately, the two sets of data are not internally consistent. Assuming that the results of their primary calculations of cohesive energies (5.05 eV atom1 for Rh17S15, 4.83 eV atom1 for Rh3S4 and 4.73 eV atom1 for

FIGURE 7. Composition dependence enthalpy of mixing for the system (Rh + S) at T = 298.15 K relative to solid Rh and solid S (ortho): d (black online), this study; j (red online), Diguez and Marzari [27]; N (green online), recalculated from Diguez and Marzari [27]. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

Rh2S3) are correct, enthalpies of formation have been recalculated, using cohesive energies of solid Rh and S from Pankratz [26]. Diguez and Marzari [27] have specied neither the values of cohesive energies of pure Rh and S used in their calculations nor the source of their data. Since the literature data on cohesive energies of Rh and S are fairly consistent, the calculated enthalpies of formation are not signicantly dependent on the source of data. The enthalpy of mixing at T = 298.15 K obtained in this study is compared with the original data reported by Diguez and Marzari [27] and values recalculated from their cohesive energies in gure 7. Although their reported values appear to be in fair agreement with the results of this study, it is the product of an incorrect calculation [27]. The values correctly calculated from their cohesive energies differ substantially from the results of this study. An important difference between the results of rst-principles calculations and experiment is the position of the minimum. Experimental data show a minimum at the composition corresponding to Rh2S3, whereas calculations place the minimum at the composition of Rh3S4. The comparison illustrates that despite recent claims of success of rst-principles approach for generating thermodynamic data, experiments still remain the most reliable route. 4. Conclusions The standard Gibbs energies of formation of three rhodium suldes, RhS0.882, Rh3S4 and Rh2S3, have been determined over the temperature range from (925 to 1275) K using a solid-state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte, and (CaF2 + CaS) as auxiliary electrodes to convert the sulfur chemical potential to equivalent uorine potential. A novel cell design is used for measurement. The results can be expressed by the following equations: Rh (s) + 0.441S2 (g) ? RhS0.882 (s),

FIGURE 6. Composition dependence Gibbs energy of mixing (DmixG) and enthalpy of mixing (DmixH) for the system (Rh + S): j (black online), DmixG at T = 1100 K; d (green online), DmixH at T = 298.15 K; X (red online), enthalpy of solid (ortho) sulfur relative to diatomic gas at T = 298.15 K; vertical arrows (red online) indicate the enthalpy of mixing (DmixH) with respect to Rh (s) and sulfur (ortho). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

Df Go RhS0:882 1030=J mol 127361 64:49 T =K;

3Rh (s) + 2S2 (g) ? Rh3S4 (s),

Df Go Rh3 S4 3445=J mol 548026 304:5 T =K;

2Rh (s) + 1.5S2 (g) ? Rh2S3 (s),

K.T. Jacob, P. Gupta / J. Chem. Thermodynamics 70 (2014) 3945

45

Df Go Rh2 S3 2335=J mol 403844 229:67 T =K:

The results obtained in this study are in reasonable accord with experimental data reported in the literature above T = 1213 K. The standard entropy (So 298:15 K ) of the three rhodium suldes estimated from the results are (60.62 3.46) J K1 mol1 for RhS0.882, (213.61 11.47) J K1 mol1 for Rh3S4 and (151.02 7.71) J K1 mol1 for Rh2S3. The enthalpy of formation from solid Rh and orthorhombic sulfur at T = 298.15 K are (74.9 3.9) kJ mol1 for RhS0.882, (311.16 12.4) kJ mol1 for Rh3S4 and (226.2 8.4) kJ mol1 for Rh2S3. These results do not support data obtained from recent rst-principles calculations [27].

Acknowledgements K.T. Jacob is indebted to the Indian National Academy of Engineering for support as INAE Distinguished Professor. Preeti Gupta acknowledges the University Grants Commission, India, for the award of Dr. D.S. Kothari Postdoctoral Fellowship. References
[1] J. Nell, J.S. Afr I, Min. Metall. (2004) 423429. [2] N.A. Vante, W. Jaegermann, H. Tributsch, W. Hnle, K. Yvon, J. Am. Chem. Soc. 109 (1987) 32513257. [3] J.M. Ziegelbauer, D. Gatewood, A.F. Gull, D.E. Ramaker, S. Mukerjee, Electrochem. Solid State Lett. 9 (2006) A430A434. [4] J.M. Ziegelbauer, V.S. Murthi, C. OLaoire, A.F. Gull, S. Mukerjee, Electrochem. Acta 53 (2008) 55875596.

[5] A.F. Gull, L. Gancs, R.J. Allen, S. Mukerjee, Appl. Catal. A General 326 (2007) 227235. [6] R.J. Allen, J.R. Giallombardo, D. Czerwiec, E.S. De Castro, K. Shaikh, US Patents 6149782, 2000 and 6358381B1, 2002. [7] R.J. Allen, J.R. Giallombardo, D. Czerwiec, E.S. De Castro, K. Shaikh, F. Gestermann, H.-D. Pinter, G. Speer, US Patent 6402930B1, 2002. [8] R.J. Allen, A.F. Gull, US Patent 6967185B2, 2005. [9] T.B. Massalski, P.R. Subramaniam, H. Okamoto, L. Kacprzak, Binary Alloy Phase Diagrams, second ed., vol. 3, ASM International, Materials Park, OH, 1990, p. 3224. [10] J.R. Taylor, Metall. Trans. B 12B (1981) 4754. [11] S. Geller, Acta Crystallogr. 15 (1962) 713721. [12] S. Geller, Acta Crystallogr. 15 (1962) 11981201. [13] B.T. Matthias, E. Corenzwit, C.E. Miller, Phys. Rev. 93 (1954) 14151416. [14] H.R. Naren, A. Thamizhavel, A.K. Nigam, S. Ramakrishnan, Phys. Rev. Lett. 100 (2008) 026404-1026404-4. ski, M.D. Welch, [15] C.J. Stanley, A.J. Criddle, J. Spratt, A.C. Roberts, J.T. Szyman Mineral. Mag. 69 (2005) 447453. [16] E. Parth, D. Hohnke, F. Hulliger, Acta Crystallogr. 23 (1967) 832840. [17] H.R. Larson, J.F. Elliott, Trans. TMS-AIME 239 (1967) 17131720. [18] R. Juza, O. Hulsmann, K. Meisel, Z. Anorg, Chem. 225 (1935) 369385. [19] K.T. Jacob, D.B. Rao, H.G. Nelson, J. Electrochem. Soc. 125 (1978) 758762. [20] K.T. Jacob, M. Iwase, Y. Waseda, J. Appl. Electrochem. 12 (1982) 5567. [21] K.T. Jacob, M. Iwase, Y. Waseda, Adv. Ceram. Mater. 1 (1986) 264270. [22] R. Akila, K.T. Jacob, Sens. Actuators 16 (1989) 311323. [23] K.T. Jacob, M. Iwase, Y. Waseda, Solid State Ionics 23 (1987) 245252. [24] M.W. Chase Jr., NISTJANAF Thermochemical Tables, fourth ed., Part I, J. Phys. Chem. Ref. Data Monograph No. 9, American Institute of Physics, Woodbury, New York, 1998, pp. 1340. [25] O. Kubaschewski, C.B. Alcock, Metallurgical ThermoChemistry, fth ed., Pergamon Press, Oxford, 1979. p. 185. [26] L.B. Pankratz, Thermodynamic properties of elements and oxides, Bulletin 672, US Bur. Mines, 1982. [27] O. Diguez, N. Marzari, Phys. Rev. B 80 (2009) 214115214121.

JCT 13350