Sept.

, 1961 Reaction of Ferric Chloride with Sodium and Potassium Chlorides 1505

hydrogen is formed from recombination of two
hydrated electrons in the water (c/. reaction 1)
H20- + H20~ —3- H2 + 20H- (11)
In acid solution the hydrated electrons can, in the
absence of other solutes with which it can react
directly as an H20“,16,17 be converted to H atoms
H20- + H+—3- + H20 (12)
which would then have to recombine to give
molecular hydrogen (reaction 1). Ce4+ ions pres-
ent in solution could be expected to compete
with the hydrogen ions for reaction ivith the hy-
drated electrons. In order to explain the decrease
of (jhz with increase in the [H+] it is possible that
either the H atoms recombine (reaction (1)) more
slowly than hydrated electrons (reaction (11)), or
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
that the rates of reactions (1) and (11) are of the
same order of magnitude but that as a result of
reaction (12) the dimensions of the spurs are in-
creased18 and the probability of like-species re-
combination reduced.
Note Added.—The results by Mahlman (J. Am.
Chem. Soc., 81, 3203 (1959)) on the determination
of G(H2) from air-free Ce4+ solutions were brought
to the attention of the author, after submission of
this paper. It does not seem possible to account
for the disagreement in our values for G(H2).
Acknowledgment.—The author wishes to thank
Drs. A. 0. Allen and . A. Schwarz for many dis-
cussions and valuable suggestions in connection
with this work.
(18) . A. Schwarz, J. M. Caffrey, Jr., and G. Scholes, J. Am. Chem.

(17) E, Hayon and J, Weiss, J. Chem. Soc., 5091 (1960). Soc., 81, 1801 (1959).
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THE REACTION OF FERRIC CHLORIDE WITH SODIUM AND POTASSIUM

CHLORIDES
By Charles M. Cook, Jr., and Wendell E. Dunn, Jr.
Pigments Department, E. I. du Pont de Nemours & Co., Inc., Wilmington, Delaware
Received February 9, 1961

The equimolar complexes of FeCh with NaCl and KC1 have been studied by phase behavior, X-ray diffraction, thermo-
chemical and vapor pressure methods. The phase diagrams show double eutectics, the FeCh-NaCl system at Xxaci = 0.48
and 0.51, and FeCl.j-KCl at 0.45 and 0.52. The standard heat of the reaction NaCl + FeCls
=
NaCl-FeCU at 25° is=

—
0.8 kcal./mole; that to form KCl-FeCls is —7.2 kcal./mole. The temperature and composition dependence of ferric
chloride pressure above its mixtures with NaCl and KC1 indicate the 1:1 complexes to be stable in the melt and to be as
M +FeCli“. Evidence is presented for the existence of NaCl-FeCl, and KCl-FeCls in the vapor phase.

Introduction servation by Dunn10 that, below 400°, the ferric

Ferric chloride is known to form 1:1 addition
compounds with molecules capable of supplying a
chloride ion, e.g., with ElqNCl,1 NH4C1,2 T1C1,3
NOCI,4 CNC1,6 P0C18,6 PCU These compounds
are regarded as containing the [FeCl4]~ ion; their
solutions in non-aqueous solvents are electrically
conducting, and electrolysis of FeCls in CNC1
transports Fe to the anode.6
Two previous studies of the FeCF-NaCI phase
diagram have indicated a single eutectic, without
evidence of compound formation.8·9 Although the
vapor pressure of ferric chloride is strongly reduced
in the presence of sodium chloride, Johnstone, et
al.,s who determined the ferric chloride pressure
above melts containing up to 46 mole % NaCl, ex-
plained this reduction as the normal effect of the
solute in lowering vapor pressure and found no evi-
dence for the existence of a compound. This ex-
planation, however, is not compatible with the ob-
(1) V. Gutmann and F. Mairinger, Z. anorg. allgem. Chem., 289,
279 (1957).
(2) K. Hachmeister, Z. anorg. Chem., 109, 145 (1919).
(3) G. Scarpa, Atti Acad. Lincei, [5] 21, 720 (1912).
(4) J. Lewis and D. B. Sowerly, J. Chem. Soc., 1617 (1957).
(5) A. A. Woolf, ibid., 252 (1954).
(6) V. V. Dadape and M. R. A. Rao, J. Am. Chem. Soc., 77, 6192
(1955).
(7) Ya. A. Fialkov and Ya. B. Burzanov, Doklady Akad. Nauk
S.S.S.R., 92, 585 (1953).
(8) H. F. Johnstone, H. C. Weingartner and W. E. Winsche, J, Am.
Chem. Soc., 64, 241 (1942).
(9) I. S. Morozov and D. Ya. Toptygin, Zhur. Neorg. Khim., 2, 2129
(1957).
chloride pressure drops rapidly to nearly zero at
50 mole % NaCl.
In the chemically similar system NaCI-AlCls
both the vapor pressure11 and phase diagram12
data are consistent in indicating the NaAlCl4
compound.
Experimental
Sample Preparation.—Two alternate procedures for
preparation of FeCl3-NaCl melts were employed. Those
FeCl3-NaCl mixtures having less than 50 mole % NaCl
that were used in measurement of the ferric chloride vapor
pressures were prepared by mixing FeCl3 (B & A Code 1733
Sublimed Technical) and NaCl (B & A, C.P.). The result-
ing mixture was treated with COCl2 for several days to re-
move traces of ferric oxide before vapor pressure measure-
ments were carried out. Melt compositions were deter-
mined at the beginning and end of each vapor pressure run
by sampling and analysis.
The ferric chloride-alkali chloride melts used for the
remaining vapor pressure, the phase diagram, and the ca-
lorimetric studies were prepared in the following manner.
Alkali chloride was added to the bulb which was to contain
the salt mixture. Air was removed by evacuation and back
filling with Cl2, and the salt was warmed to 300°. Iron
wire, contained in a side tube attached to this bulb, was
burnt in a stream of chloride, and the ferric chloride sub-
limed into the salt. The traces of iron and alkali chloride
carried by the chlorine from the pot during sample prepara-
tion were trapped in a Pyrex wool plug located before the
exit bubbler and were determined by analysis. The melt
(10) W. E. Dunn, Jr., presented at A.C.S. Delaware Valley Regional
Meeting, Feb. 16, 1956.
(11) E. W. Dewing, J. Am. Chem, Soc., 77, 2639 (1955).
(12) U. J. Shvartsman, Zhur. Fiz. Khim., 14, 254 (1940).
1506 Charles M. Cook, Jr.,
compositions were determined from the weights of salt and
iron put into the mixture.
The sodium chloride and potassium chloride were purified
by fusion in HC1 and were crushed and stored under a dry
atmosphere. The iron wire was Baker Analyzed reagent
grade; the chlorine was Matheson “oxygen-free.”
In subsequent discussion where melt compositions are
expressed as mole fraction of alkali chloride, MCI, this is an
input or nominal mole fraction; Xmci JV input MCl/A"
= The sample was sealed into a Pyrex ampoule and this was
input MCI + N input FeCl3. The mole fractions of MFe-
Cl4, on the other hand, are believed to represent the actual
concentrations of MFeCl4 in the melt and are calculated
presuming reaction 2 to be quantitative. In MCl-rich
melts XiiFecu Ar input FeCl3/Ar input MCI.
= The tube furnace was constructed of an electrically heated,
Phase Diagrams.—The salt mixtures used in the phase
studies were prepared in 30 mm. d. by 4" Vycor bulbs and
were sealed off under a Cl2 pressure of 90 mm. The bulbs
were then placed inside a cavity, formed of “TIPERSUL”
insulation, inside a 7" length of 2.5" d. heavy wall steel pipe
located within a well-insulated tube furnace. Agitation
of the molten mixture was provided by rocking the tube
furnace.
The transition temperatures of the salt mixtures were
determined from their cooling curves. Salt temperatures
were measured by a Chromel-Alumel thermocouple, which
had been standardized previously against the melting point
of bismuth, located in a well along the axis of the bulb.
The phase transitions were located by following the tem-
perature differential between sample and surrounding pipe,
measured by two pairs of Chromel-Alumel thermocouples,
on a Minneapolis-Honeywell Brown recorder. Changes in
cooling rate appeared as sharp discontinuities in the slope
of the differential temperature vs. time plot. Transforma-
tion temperatures measured by this method were repro-
ducible to ±1° below 250° and to ±2° for higher tem-
peratures.
X-Ray Powder Patterns.—Mixtures of NaCl-FeCls and
KCl-FeCls were taken from the sample bulbs after cooling
curves were run, ground in a dry box and loaded into 0.5
mm. Lindemann glass capillaries and exposed to iron filtered
35 Kv. cobalt radiation for four hours in a powder camera.
The D spacings were read from the Debye-Scherrer photo-
graphs with a Mies scale, and the intensities of the lines were
estimated visually.
Calorimetric Measurements.—The solution calorimeter
was a one-liter Dewar flask closed with a cork through which
were brought a Beckmann thermometer, a stirrer, and tube
for introducing samples. The calorimeter contained 800
cc. of HC1 + XaCl + KC1 solution in which the ferric chlo-
ride-containing salts were readily soluble. The water
equivalent of the calorimeter plus the solution was measured
by observing the temperature rise per watt minute passed
through a resistor inside the calorimeter.
Approximately 10-g. samples of XaCl, KC1, FeCls,
XaFeCh and KFeCh were loaded in a dry box into glass
bottles which were then paraffined and stored in a desic-
cator until use. The FeCls had been purified by sublima-
tion in Cl2; the XaFeCh and KFeCh had been prepared and
used in the phase studies. These salts were stored in sealed
bulbs until this use.
A sample bottle was weighed, the calorimeter entry tube
unstoppered, the sample quickly uncapped and dumped
through the tube into the HC1 solution, the calorimeter
closed and the emptied bottle reweighed. In this process
the salts were exposed to the atmosphere for less than three
seconds. Heats of solution were determined from the tem-
perature change. The calorimeter was operated near room
temperature; thus corrections for the sensible heat intro-
duced with the salt were small.
Measured heats of solution were
in 4.92 A' HC1
XaCl —
—2.2 kcal./mole
KOI =
—4.0 kcal./mole
FeCls —
20.8 kcal./mole
XaFeCh 18.1
=
kcal./mole
KFeCh 9.6 kcal./mole
=
in 6.14 A HC1, 0.125 N XaCl, 0.125 N KOI
XaCl —2.3 kcal./mole
=
KC1 = —3.9 kcal./mole
FeCls 18.8 kcal./mole
=
XaFeCh =
15.6 kcal./mole
KFeCh =
6.8 kcal./mole
and Wendell E. Dunn, Jr. Vol. 65
Heats of fusion and heat capacities were determined in
a drop calorimeter constructed in the same fashion as the
solution calorimeter except that the entry port was re-
placed by a Pyrex test-tube and the calorimeter contained
H20 rather than HC1 solution. The test-tube, extending
into the water, was padded on the bottom with a plug of
Pyrex wool and contained 10 cc. of silicone oil to facilitate
heat transfer.
suspended by a fine copper wire inside a tube furnace.
The sample temperature was measured with a Chromel-
Alumel thermocouple placed in a thermocouple well extend-
ing about three-quarters of the way into the ampoule.
asbestos-jacketed, 3/4" by 11" 1. copper pipe. The top
of the furnace was sealed with an asbestos plug through
which passed the sample thermocouple and the copper wire
suspending the ampoule. In the region of the sample the
furnace wall temperature was uniform to ±2°.
When the sample had come to constant temperature, the.
tube furnace was swung into position over the calorimeter,
an aluminum radiation shield removed, and the sample
dropped into the test-tube by cutting the copper wire.
The furnace then was removed and the test-tube corked.
Because of the short time of exposure and the relatively
low temperatures employed, radiative heat transfer from
the furnace to the calorimetric during the release of the
sample was not significant.
The heat content of the Pyrex in the ampoule was calcu-
lated assuming that for Pyrex Cp 0.20 cal./g.
=
For calibration, the heat contents of a sample of bis-
muth were determined at two temperatures using the drop
calorimeter with the above procedure.
Obsd.
Temp., Tt —
Hi do Actual Ht —
Hi oc,13
cal./mole cal./mole
1470 1460 ± 30
518
584 4550 4560 ± 80
Vapor Pressure.—The pressures of FeCls and MFeCh
above ferric chloride-alkali chloride mixtures were measured
by a transpiration method. The molten salts were con-
tained in a long-necked Vycor flask immersed in molten
solder. The carrier gas, Cl2 at 40-120 cc./min., was
brought into the melt by a side arm sealed to the flask.
For melt temperatures in excess of 6000 the Cl2 was preheated
with a Xichrome winding around the side arm before it
passed through the solder bath into the Vycor flask. After
bubbling through the melt the Cl2 passed through a con-
denser and was exhausted through a bubbler. Cl2 flow was
measured by capillary flowmeters or by titration of I2 liber-
ated from KI solutions.
The condenser was a Vycor tube sealed at the one end to a
standard taper grind and formed at the other end into a cup
to trap any liquid running down the inside surface. The
condenser was inerted through the neck of the Vycor flask,
the grind sealing to a corresponding grind on the neck
of the flask, the cup extending down into the heated zone.
A plug of Refrasil wool in the condenser opening at the
cup end prevented splattered melt from being carried by
the Cl2 into the condenser.
In a typical run the condenser was flushed with Cl2 and
inserted into the flask. A constant flow rate of Cl2 was then
bubbled through the melt for a known time, after which the
condenser was removed and the deposited chlorides washed
out and analyzed for Fe (by Volhard procedure) and Na
(with zinc uranyl acetate) or K (with NaBPh4). An argon
purge, entering through a side arm in the neck of the flask,
blanketed the melt during changing of condensers.
The observed data, the moles of Fe(III) and M(I) trans-
ported per mole CI2, were converted to vapor pressures on
the assumption that the gas phase species were FeCI3(g),
Fe2Cl6(g) and MFeCl4(g). Duplicate runs at different Cl2
flow rates indicated the vapor pressures to be independent
of CI2 flow.
The vapor pressure data are presented as PFeci/, the com-
bined vapor pressures of ferric chloride monomer and
dimer, and as PaFeou, the vapor pressure of the presumedly
monomeric complex.
(13) O, Kubashchewski and E. Evans, "Metallurgical Thermochem-
istry,” 2nd Ed,, John Wiley and Sons. New York, N. Y., 1956,
Sept., 1961 Reaction of Ferric Chloride with Sodium and Potassium Chlorides 1507

Fig. 1.—Partial solid-liquid phase diagram of the system Fig. 2.—Partial solid-liquid phase diagram of the system
FeCls-NaCl. Eutectics at XnsCi =
0.48, 157°; Xn»ci =
FeCh-KCl. Eutectics at Xkci 0.45, 206°; Xkci
= =

0.51, 162°. Congruent m.p. = 163°. 0.52, 242°. Congruent m.p. = 249°.

Discussion
Phase Data.—Figures 1 and 2 show the phase
diagrams of FeCls-NaCl and FeCl3-KCl in the
regions between 40 and 60 mole % FeCl3. Both of
these diagrams are seen to be consistent with the
formation of a congruently melting 1:1 compound.
The low melting point of NaFeCh causes the FeCl3-
NaCl phase diagram to resemble that of a simple
eutectic; the existence of the compound is appa-
rent, however, in the consistent 4.5° difference in
eutectic temperatures above and below X^aci =

0.50. The higher melting KFeCl4 shows clearly as

a congruently melting compound in the FeCl3-KCl
system.
A poorly-defined solid state phase transformation
occurs at ~156° in the FeCl3-KCl system.
The existence of the compounds NaFeCl4 and
KFeCh was confirmed by X-ray patterns of the
powdered salt mixtures. A complex pattern of
lines was observed, with the most intense occurring
at 3.18, 3.02, 2.91, 2.82, 2.43, 2.26, 2.24, 2.07, 1.76,
1.72 and 1.55 A. for NaFeCl4oand at 3.86, 3.70,
2.75, 2.66, 2.48, 2.36 and 1.74 A., for KFeCl4. In
addition to the MFeCh patterns, in mixtures con- Fig. 3.—Relative enthalpies of NaFeCh and KFeCh-
taining more than 50 mole % alkali chloride NaCl or Reaction 1 is exothermic for NaFeCh (c) and KFe-
KC1 lines appeared strongly. For mixtures with
less than 50 mole % alkali chloride the pattern of Cl4(c), although for the former the heat effect is
ferric chloride was present and alkali chloride lines slight.
AH°(i,Na) =
—0.8 ± 0.6 kcal./mole
appeared only weakly if at all.
Calorimetric Data.—The difference between the AHQ(i.k) = —
7.2 ± 1 kcal./mole
heats of solution in aqueous HC1 of MFeCh(c) and The difference in exothermicity between K and Na
of MCl(c) plus FeCl3(c) is //0 , )> the enthalpy salts is in part due to the smaller lattice energy14
change at 25° of the reaction of KCl(c) ( 169.9 kcal./mole).
—

MCI(c) + FeCls(c) =
MFeCh(c) (1) (14) D. Cubicclotti, J. Ckem. Phys., 33, 1579 (1960).
1508 Charles M. Cook, Jr., and Wendell E. Dunn, Jr. Vol. 65

Fig. 4.—Vapor pressures oí NaFeCh and KFeCh: 6, Ansci 0.514; O, Afitaei

=
0.540; =
@, Afijaci =
0.575; O, An,ci =

0.650; X, A'kci 0.525; +,

—
0.575. =

Figure 3 shows the variation with temperature of will have enthalpy change
molar heat content of NaFeCh and KFeCh meas- Aff(2,M) °( , ) + [A#F(MreCl4>
= -

AffF(FeCI«) -

ured with the drop calorimeter. The values of heat

capacities and heats of fusion, determined from the
. (µ )] (298) + J^gg[ACp<n<i) —

(7 < ) 5 (3)
slopes of the lines and from the step heights in this Substitution of the heat of fusion15·18 and heat
figure, respectively, are in Table I. capacity17 values for MCI, FeClg and MFeCh into
Table I (3) yields
Cp solid,
cal./mole
Cp liquid,
cal./mole
AH Fusion,
kcal./mole
AS Fusion,
e.u./mole
, .) = -7600 -
5.35T cal./mole,
Compd. °C. °C. 300°K. < T < 600°K.
NaFeCh 39.5 42.1 4.30 9.86 áHq,k) = —19900 + 5.81 T cal./mole,
KFeCh 40.0 53.0 3.85 7.36 300°K. < T < 600°K.
(15) N.B.S. Circular 500, “Selected Values of Chemical Thermo-
The above thermodynamic values indicate that “
dynamic Properties, 1952.
the te trac hlorof erra te complex should form ex- (16) The values A#(6ao.7) (FeCls Fusion) = 9 d= 0.4 kcal./mole
othermically, not only in the solid state, but also in FeCla and ?(68 .7) (FeCls Vap.) = 14.9 dz 0.8 kcal./mole FezCIe are
the melt. Thus, at temperature T°K., the reac- used herein. C. M. Cook, Jr., unpublished work.
(17) Cp values are from K. K. Kelley, “Contributions to The Data
tion on Theoretical Metallurgy. XIII," Bulletin 584, U. S. Bureau of
MCl(liq) + FeCb(liq) MFeCh(liq)
=
(2) Mines (1960).
Sept., 1961 Reaction of Ferric Chloride with Sodium and Potassium Chlorides 1509

for the liquid state reaction of the sodium and potas-

sium salts, respectively.
Vapor Pressure. MFeCh.—Chlorine passing
through a ferric chloride-alkali chloride melt trans-
ports, in addition to ferric chloride, appreciable
quantities of sodium or potassium salts. Since
pure NaCl or KC1 is not significantly volatile
within the experimental temperature range, and
since the Fe(III)/M(I) ratio transported is never
less than unity, it appears reasonable that the
vapor above the melt contains a complex species,
probably MFeCfi. Dewing11 has reported vola-
tilization of NaAlCU from AlCl3-NaCl melts and
Porter and Zeller18 find LiAlF4(g) above molten
AlF3-LiF.
For melts at constant composition the logarithms
of the vapor pressures of NaFeCl4 and KFeCL¡
vary linearly with reciprocal temperature as is
shown in Fig. 4. The plotted points are the observed
vapor pressures divided by the XMFeCU in the melt.
The solid line represents the least squares fit of the
PNaFeci. data, the dotted line of the PKFeCi,
data. The partial pressures of MFeCl4 over liquids
of nominal composition MFeCL¡ are calculated to be
log Pn„f=cl (mm.) = 7.496 -
5904T~i
750°K. < T < 1100°K.
log ß (mm.) = 4517 "1
5.657 -
0 10 20 30 40 50
850°K. < T < 1100°K. Mole % NaCl.
Ferric Chloride.—Ferric chloride vapor below Fig. 5.—Vapor pressure of ferric chloride above FeCls +
NaCl mixture at 352°: O, Stirneman; e, Johnstone, et
400° exists primarily as the dimer, Fe2Cle(g), and al·, this work.
above 600° as the monomer, FeCla(g). The
equilibrium is Fig. 6. The straight lines, which are least squares
2FeCl9(g) Fe„Cl6(g) (4) averages of the Precis* vs. T~l data at constant com-
=

with13 position, show, for melt compositions below 50 mole

A if" -32.55 kcal., AS"
= =
-31.65 e.u.; % NaCl, slopes approximately parallel to the slope
778°K. < T < 998°K. of the FeCls liquid vapor pressure curve given by
Stirneman20; above 50 mole % NaCl the slopes
Within the experimental temperature range, 250- steepen. The KCl-containing melts exhibit lower
750°, ferric chloride vapor will be present both as ferric chloride vapor pressures and steeper d log
monomer and dimer. For convenience in presenta-
PreCi.VdT-1 slopes than similar NaCl melts.
tion the ferric chloride pressures in equilibrium In Table II concentration equilibrium constants
with the FeCla-MCl melts are expressed in Fig. 5 for the reaction
and 6 as a combined pressure of monomer and dimer
i.e. MFeCU(soln) =
MCl(soln) + FeCl,(v) (6)
P FeClj + are presented for FeCla-MCl mixtures containing
PFeCL* =
2Pre2Cl« (5)
excess alkali chloride. The approximate constancy
Addition of NaCl to ferric chloride brings about of the Keq values is consistent with the formation of
a steep, titration-like decrease in vapor pressure to
the MFeCl4 species.
almost zero at 50 mole % NaCl. As shown in Fig.
5, at 352° the vapor pressure drops by 2.5 orders of Table II
magnitude as the melt composition changes from 45 Equilibria at I000°K. According to Reaction 6
to 50 mole % NaCl. This behavior is consistent FTeq —
XMCl
with the existence in the melt of a 1:1 compound Mole % MCI X.MFeCU Precis, mm.
RFeC13/
XMFeCU
between FeCls and NaCl. 54.0 NaCl 0.855 73.3 12.0
The solid and the dashed curves in Fig. 5 repre- 57.5 NaCl 37.2
.739 13.0
sent the Precis* composition dependence anticipated 65.0 NaCl .539 18.8 16.0
if the unreacted ferric chloride is dissolved in the 52.5 KC1 .905 24.3 2.6
ionized NaFeCl4 melt as Fe2Cle or as FeCls, re- 57.5 KC1 .739 7.46 2.6
spectively, and if Raoult’s law is obeyed.19
The dependence upon temperature of ferric chlo- As a check of agreement between calorimetric and
ride pressure above FeCIa-MCI melts is shown in vapor pressure data it is instructive to compare
(18) K. F. Porter and E. E, Zeller, J. Chem. Phys., 33, 858 (1960). enthalpies of solution of ferric chloride in MFeCl4
(19) The FeCb-NaCl liquidus temperatures of Johnstone, et al., are derived from the slopes of the curves in Fig. 6
ca. 10° higher than the freezing points calculated from d In XFejCle/
dr-1 *= —
/R presuming = 18 kcal./mole FezCls and the
with the enthalpies of reaction 2. From the d log
f.p. of Fe2Cle «= 307.5®, This temperature difference indicates TFegCIe (20) E. Stirneman, Neues Jahrb. Min. Geol. Paleontology, 52, 334,
~
1.5 at 290®. 353 (1925).
 1510 Charles M. Cook, Jr., and Wendell E. Dunn, Jr. Yol. 65

100

mm.

PvcCh1,

Fig. 6.—Temperature dependence of ferric chloride vapor pressure above FeCl3 + NaCl and FeCl3 + KCI mixtures.
PrecD/cCr-1 values of Fig. 6 the enthalpy changes, Table III
AH(rj's, of the reaction Estimation of The Heat of Solution of FECl3(iiq) in
FeCl3‘(g) =
FeCl3(soln) (7) Molten MFeCh + MCI Mixtures from d loo PFeci//
(Í.C., AH(n)); AND FROM Calorimetr] :c Data (i.e..
1

can be obtained at the several melt compositions.

—15 cal./mole °, the enthalpy AH( i.M))
f

Assuming ACp® =

Vx.fi Axx temp., °K. ai), kcal. AH(2, Xai, kcal.

of vaporization
0.472 630 + 1 0
FeCls(liq) =
1/2 Fe,Cl6(g) (8) .484 640 + 1 0
(s) 16160 15T cal./mole
= —

.499 830 -8 0
combined with the enthalpy of reaction 4 at 888°K. .514 810 1
O -12
yields for .540 950 -10 -13
.575 980 -12 -13
FeCl„(liq) FeCl,(g)
=
(9)
.650 1050 -10 -13
All(9) 19 kcal./mole
=
X kci Axx temp. Aff(ii) AH(2 K)
An average enthalpy of vaporization, AH a 0), can 0.525 970 -16 -14
be computed for a series of Preci/ data points at 0.575 1000 -25 -14
constant composition by combining ® and FeCls(liq) =
FeClahg) (10)
AH(-¿) in proportion to the average fraction of the AH(10) =
2AHi$) [P ß2015/( ß 0 6 + -PFecdavg. +
IACl/ present as Fe8Clt and FeCl3, respectively. AH(9) ÍPleCu/(Pw<nOh +PFeClsllavg.
Sept., 1961 E.m.f. Measurements in Molten Bismuth-Bismuth Trichloride Solutions 1511

Adding equations 7 and 10 approximate AH a, ml In Table III the values of

AH(id calculated from the log (vapor pressure) -

FeCls(liq) =
FeCI3(soln) (11) temp.-1 slopes are compared with the values of
AH{ id =
( 7) + ( ) AH(2,m) calculated from the calorimetric data and
equation 3. In view of the uncertainties introduced
yields £ ;U), the apparent heat of solution of with measurements of slope and with the 400° ex-
liquid FeCi3 in the melt as derived from the slope trapolation of reaction 2 the agreement between
of the vapor pressure curves. AH cm and AH( 2,m> is satisfactory. The apparent
Now if indeed it is true that ferric chloride reacts disagreement in the last KC1 series is possibly the
with sodium chloride according to reaction 2, result of analytical error in the pair of points at ~
then for initial FeCF/MCl mole ratios greater than —

1.11; if these are omitted the AH an derived

unity AHai) should be approximately zero, and from the least squares slope of the remaining points
for FeCF/MCl ratios less than unity AH( should is —18 kcal., in better agreement with 7(2, >

E.M.F. MEASUREMENTS IN MOLTEN BISMUTH-BISMUTH TRICHLORIDE

SOLUTIONS1
By L. E. Topol, S. J. Yosim and R. A. Osteryoung

Atomics International, A Division of North American Aviation, Inc., Canoga Park, California
Received February 27, 1961

E.m.f. studies on cells of the type C, Bi(JVi), BiCl3(l 5) [|BiCl3(l N2), Bi(Y2), C where N denotes mole fraction,
— —

were made at 238, 270, 300, 325 and 350°; also, the effects of varying acidity were observed by examining a cell containing
a 70 mole % BiCl3-30 mole % KC1 melt at 325°, and another with a 75% BiCl3-25% A1C13 melt at 270°. The Bi concen-
tration Ni in the reference half-cell was held constant, and the Bi concentration N2 in the other half-cell was varied from 0 to
about 0.06 by coulometric addition. A cell containing higher concentrations, i.e., N2 0.07 to 0.25, was studied in a
=

similar manner. Plots of the e.m.f. vs. log Bi concentration yielded initially straight lines which changed slope at low metal
concentrations, i.e., N2 < 0.01; the metal concentration at which this departure from linearity occurred increased with
temperature and with the acidity of the system. For the low concentration region a slope corresponding to a Nernst n of
2.05 ± 0.10, consistent with the species Bi+, was found at all temperatures. The data for the higher Bi concentrations, i.e.,
N2 > 0.01, are interpreted in terms of the species BÍ4CI4. The equilibrium constant, , for the reaction 4BÍC1 BÍ4CI4 =

can be expressed as log Ky [(4.49 ± 0.54) X 103]/ ° .

= 1.930 ± 0.945 for Ab¡ < 0.09 and the temperature range 238
—

to 350°.

Introduction (for which 2.0) as the most probable entity at

=

Although the phase diagram2·3 and properties4-7 low bismuth concentrations.

of the bismuth-bismuth trichloride system have
been investigated, the mode of solution of the metal
in its molten salt is still uncertain. The solid
subhalide BiCl has been isolated,8 and a cryoscopic
study96 yielded results which were consistent with
the species Bi2Cl29a’b in solution. In a recent
polarographic study10 it was found that in BiCl3
melts containing low concentrations of bismuth (less
than 0.002 mole fraction) the species resulting
from solution of the metal could be oxidized, and
this reaction appeared to be reversible at an inert
electrode. In addition, an analysis of the polaro-
grams yielded apparent Nernst n’s of 1.5-1.8.
These results, although inconclusive, suggest Bi+
(1) This work was carried out under the auspices of the Research
Division of the Atomic Energy Commission.
(2) . A. Sokolova, G. G. Urazov and V. G. Kuznetsov, Akad.
Nauk, S.S.S.R., Inst. Gen. Inorg. Chem., 1, 102 (1954).
(3) S. J. Yosim, A, J. Darnell, W. G. Gehman and S. W. Mayer,
./. Phys. Chem., 63, 230 (1959).
(4) D. Cubicciotti, F. J. Keneshea, Jr., and G. M. Kelley, ibid.,
62, 463 (1958).
(5) F. J. Keneshea, Jr., and D. Cubicciotti, ibid., 62, 843 (1958).
(6) . A. Bredig, H. A. Levy, F. J. Keneshea and D. Cubicciotti,
ibid., 64, 191 (1960).
(7) A. J. Darnell and S. J. Yosim, ibid., 63, 1813 (1959).
(8) J. D. Corbett, J. Am. Chem. Soc., 80, 4757 (1958).
(9a) S. W. Mayer, S. J. Yosim and L. E. Topol, J. Phys. Chem., 64,
238 (I960).
(9b) . A. Bredig, ibid., 63, 978 (1959).
(10) L. E. Topol and R. A. Osteryoung, J, Elect roc hem. Sor... 108,
573 (1961).
In conjunction with the polarographic work
above, an e.m.f. study was performed on this
system. The potentiometric method has been
utilized with apparent success in the Cd-CdCl2-
KC1,11 Li-LiCl,12 Pb-PbCl2,u Ce-CeCl314 and
Sb-Sbl315 systems, and appropriate concentration
cells should yield more conclusive information as
to species in Bi-BiCl3 solutions at low bismuth
concentrations. In addition, the effect of changes
in acidity was investigated by the addition of A1C13,
in one case, and KCI, in another, to the system.
Experimental
Materials.—The purification of most of the materials
used hasbeen described elsewhere.3·10 Reagent grade
KCI was dried by heating at 600° under vacuum. Anhy-
drous AICI3 was prepared by repeated sublimation of the
reagent grade salt in vacuo.
Apparatus and Procedure.—The cells and procedure em-
ployed in the bulk of this work were similar to those used in a
polarographic study.10 However, the e.m.f. cells differed
from these in that they usually incorporated several reference
half-cells; the reference half-cells contained weighed amounts
of Bi and BiCl3 to give metal mole fractions of 0.0025, 0.005
(11) S. Karpachev and A. Stromberg, Zhur. Fiz. Khim., 13, 397
(1939).
(12) S. Karpachev and E. Jordan, ibid., 14, 1495 (1940).
(13) S. Karpachev, A. Stromberg and E. Jordan, ibid., 18, 43
(1944).
(14) S. Senderoff and G. W. Mellors, J. Electrochem. Soc., 105,
224 (1958); cf., however, H. R. Bronstein, A. S. Dworkin and . A.
Bredig, J. Phys, Chem., 64, 1344 (1960).
(15) J. Corbett and F. C, Albers, J. Am. Chem. Soc., 82, 533 (I960).