Professional Documents
Culture Documents
Contents
I. Introduction....................................................................... 177
II. The Isoelectric Points of Solid Oxides and Hydroxides.................................... 178
A. Selection and Presentation of Data................................................ 178
1. General..................................................................... 178
2. Aluminum Oxides and Hydroxides.............................................. 178
3. Quartz and Silica Gels........................................................ 178
B. Variables Affecting the Isoelectric Point............................................ 178
1. Gross Effect of Cationic Charge................................................ 178
2. Effects of Hydration.......................................................... 184
3. Effects of Impurities........................................................... 186
4. Nonstoichiometry, Defect Structures, and Semiconductors......................... 187
C. Variation of IEPS with Cationic Size and Charge................................... 188
1. An Electrostatic Model........................................................ 188
2. Coordination Number Six and Crystal Field Effects............................... 189
3. Coordination Number Four.................................................... 190
4. Coordination Number Eight................................................... 190
5. Summary.................................................................... 190
III. The Isoelectric Points of Aqueous Hydroxo Complex Systems............................ 191
IV. Comparison of the Isoelectric Points of Solids with Those of Hydroxo Complex Systems....... 192
A. General Observations............................................................ 192
B. Adsorption and Identification of Potential-Determining Species........................ 192
C. Alternate Mechanisms for Potential-Determining Ion Adsorption....................... 194
1. Adsorption onto Hydrogen-Bonded Water....................................... 194
2. Nonequivalence of Potential-Determining Species................................. 194
3. pH-Dependent Surface Modification............................................ 195
V. Summary and Conclusions.......................................................... 195
VI. References........................................................................ 195
Solid oxides in aqueous suspension are generally The term “IEPS” will be used when referring to
electrically charged as may be observed most directly solids and “IEP” when referring to dissolved species.
in electrophoresis experiments. The charge has long The IEPS and the ZPC are identical by definition.
been attributed to one of two apparently indistinguish- Based primarily on data for the W(VI) and Fe(III)
able mechanisms (5-7, 36, 56, 81, 87, 129): (a) am- systems it was proposed in 1962 (87) that the IEPS was
photeric dissociation of surface MOH groups; and (b) identical with the IEP of the corresponding hydroxo
adsorption of metal hydroxo complexes derived from complexes. The evidence readily available at that
the hydrolysis products of material dissolved from the time was convincing but meager. A much more ex-
solid, i.e., from amphoteric dissociation of Mz+(OH)2- tensive collection of IEPS’s and IEP’s has been com-
(aq). piled to serve as a reference list and to test whether or
Both mechanisms explain qualitatively the pH de- not the two are indeed equal.
pendence of surface charge and the existence of a pH This paper is concerned first with the isoelectric
resulting in zero net charge, called the isoelectric point points of solid oxides and an analysis of the dependence
(IEP) or zero point of charge (ZPC). The term “iso- of the IEPS on the properties of the cation, its coordina-
electric point” is variously used to represent both the pH tion, the hydration state of the solid, and its purity.
at which an immersed solid oxide surface has zero net The second major concern of the paper is comparison
charge and the pH resulting in (electrically) equivalent of the IEPS’s with the isoelectric points of appropriate
concentrations of positive and negative complexes, i.e. hydroxo complex systems and a discussion of the rela-
( -
II. The Isoelectric Points of Solid because the high frequency of recurrence of the “cluster
Oxides and Hydroxides values” seems to indicate that each does indeed have
a. selection and presentation of data real meaning. Detailed citations for each system are
given in Tables II, III, IV, and V.
1. General
Many methods have been used to estimate the IEPS. 2.Aluminum Oxides and Hydroxides
Electrokinetic methods, including electroosmosis, IEPS’s for “amorphous” Al(OH)3, “hydrous” A1203,
streaming potential, and electrophoresis, are used and for well-characterized a and 7 forms of A1203,
commonly enough to require no further description. AlOOH, and Al(OH)3 are given in Table II. A citation
Direct measurement of potential-determining ion ad- frequency analysis of the IEPS reported for each mate-
sorption by potentiometric titration (19, 83a, 87) and rial was made. Replicate measurements on one mate-
study of the pH dependence of nonspecific adsorption rial in the same laboratory were considered once.
are important, less commonly used methods. The Measurements on one material in one laboratory but
IEPS may be inferred from a great variety of other by several methods were considered independent.
measurements because much of the behavior of near- Robinson, Pask, and Fuerstenau (103) have shown
colloidal suspensions depends upon the structure of the that heat treatment of synthetic - 1203 decreases the
electrical double layer which is absent or collapsed at IEPS to a value near pH 6.7. Subsequent aging for 7
the IEPS (83a, 129). days under water led to values near 9.2. Holmes (86)
All of the IEPS data available to the author are found an intermediate value after an indefinite water-
summarized in Table I. The entries listed under each aging time (< 1 day); hence, his value was rejected as
element are arranged chronologically, the most recent failing to represent any equilibrium state of the solid.
first. Whenever possible, details of sample preparation The observations on natural minerals by Schuylenborgh
and characterization, measurement method, and experi- and Sanger (111, 112) have not been reproduced by any
mental conditions are given. In one case details are other group, hence are questioned but not rejected, be-
sufficiently complex to merit special mention. Mattson cause their method is valid (1) and IEPS’s for many of
and Pugh (72) prepared hydrous oxides by mixing ap- their synthetic materials agree with observations by
propriate metal salts, usually the chloride, and HC1 or others.
NaOH as necessary to vary pH in resulting suspensions. IEPS determinations on amorphous materials are
Electrophoretic velocities were measured in the same accepted only with reservation owing to the uncertainty
suspension after aging for approximately 12 hr. Thus of structure and to the very high probability of anion
the material for which the IEPS is reported has been coprecipitation (124). When first precipitated, cold
precipitated at the IEPS and still contains whatever amorphous aluminum hydroxide is probably hydrous
coprecipitated anions were present during precipitation. 7-AIOOH. On aging cold, transition from 7-AIOOH
No attempt was made to identify the solid by X-ray to - and to a-Al(OH)3 occurs. On aging hot
diffraction. Only in the case of A1203 and Fe203 were (~100°), 7-AIOOH crystals grow and lose adsorbed
the solids chemically analyzed. water. Thus amorphous materials are probably mix-
IEPS’s considered questionable for any reason are set tures of hydrous 7- and - and a-Al(OH)3 (124).
off in parentheses. In general, all of the IEPS’s listed The average IEPS’s (cluster averages) for each oxide
in Table I are used in the analyses to follow. However, and hydroxide of aluminum are summarized in Table I.
the most basic IEPS’s for Zr02 and Th02 are omitted Further discussion of these materials will appear under
because of the high probability that specific adsorption
“Hydration” and “Effects of Impurities” below.
of cations has occurred in these cases. The IEPS’s of
Mn(OH)2 and Sn(OH)2 are omitted because special 3. Quartz and Silica Gels
precautions should be taken to prevent oxidation of the IEPS citations for Si02 are listed in Table IV. Ex-
hydroxides, and no such precautions are mentioned by cluding citations stating that the IEPS is less than “X”
the experimenter. pH, natural quartz has an average IEPS of pH 2.2 and
Many IEPS citations were found for the four oxide gels and sols an average of pH 1.8. The difference is
systems Al (III), Fe(III), Si(IV), and Ti(IV). When the probably not significant, hence an IEPS less than or
frequency of recurrence of an IEPS among independent equal to pH 2.0 ± 0.2 should be assumed.
citations for each well-characterized material was
studied (“citation frequency analysis”), several clusters b. variables affecting the isoelectric point
of values were observed. Although, by definition, one
1. Gross Effects of Cationic Charge
IEPS characteristic of each different material would be
expected, the average of each cluster (which includes Broad probable IEPS ranges characteristic of the
two or more independent citations) is taken as a signifi- cation oxidation state may be selected from Table I as
cant apparent IEPS for the material. This is done shown in Chart I.
Isoelectric Points of Solid Oxides and Hydroxides 179
Table I
Isoelectric Points of Oxides and Hydroxides0·1
Material IEPS Comment Investigator Ref.
Aluminum
a-AlaOs 5, 6.6, 9.2 \
7-Al2Oa (8.0) f
«- (7.7), 9.1 > See Table II
tt-Al(OH), 5.0 \
- ( ), 9.25 /
Antimony
Sb206 «0.4) un, IEPS by eo Michaelis 75
Beryllium
BeO (hydrous) (10.2) un, IEPS by eo Michaelis 75
Cadmium
Cd(OH)2 (>10.5) un, ppt. from CdCl2 + KOH, w, a, prod- Holmes 86
uct Cd(OH)2 or CdO(hyd), IEPS by
mep.
CdO (10.4 ± 0.2) Cd(OH)2, ig., x (contains ~5% Cd3Si06· Holmes 86
2H20), IEPS by mep.
Cerium
Ce02 (hydrous) (6.75) un, ppt CeCl4 + NaOH, IEPS by mep, in Mattson and Pugh 72
µ est. = 0.02 M
Chromium
Cr2Oj (hydrous) (7.0) ppt CrCl3 + NaOH as descr. IEPS by Tewari and’Ghosh 119
mep. If 10% excess NaOH: w, IEPS
=
6.49; w, a (4 mo. at room temp.),
IEPS 6.96; w, a (temp > room
=
Cobalt
Co(OH), (—11.4) un, ppt CoCl2 + NaOH, IEPS by mep. in Mattson and Pugh 72
µ est. 0.01 M
=
Copper
1. Blue ppt from Cu(N03)2 + NaOH (0°) Holmes 86
identified by color only, w (0°), a (0°)
Cu(OH)j (9.4 ± 0.4) un, IEPS by mep. (0°)
CuO 9.5 ± 0.4 x, w, a (100°), a, IEPS by mep. (room
temp.)
2. Cu(OH)2 (hydrous) (7.6) un, ppt CuCl2 + NaOH, IEPS by mep. in Mattson and Pugh 72
µ est. <0.01 M
Iron
1. Fe(OH), (12 ± 0.5) un, IEPS by eo Krause and Borkowska 64
2. FeaO« 6.5 ± 0.2 Natural magnetite (Port Henry, N. Y.), Iwasaki, Cooke, and Kim 54
dry ground only, IEPS by mep.
3. FegO* 6.5 ± 0.2 Synth, by reduction natural Fe203 in CO- Iwasaki, Cooke, and Kim 54
C02, IEPS by mep.
4. a-Fe203 5.2, 6.7, 8.6 \
7-Fe203 6.7 ±0.2 /
a-FeOOH 6.7 ± 0.2 > See Table III
7-FeOOH 7.4
“Fe(OH)3” (amorph) 8.5 )
Lanthanum
La2Oj (hydrous) (10.4) un, ppt LaClj + NaOH, IEPS by mep. at Mattson and Pugh 72
µ est. = 0.01 M
180 George A. Parks
Table I (Continued)
Material IEPS Comment Investigator Ref.
Lead
1. Pb(OH)2 (9.8 ± 0.5) un, white ppt dil. Pb(N02)2 + NaOH, w, Holmes 86
a, Pb(OH)2 + tr PbCO,-2Pb(OH)2 (x),
gave ZPC = 11.6 ± 0.2, IEPS by mep.
2. Pb(OH)2 (11.0) un, ppt Pb(NO,)2 + NaOH, IEPS by Mattson and Pugh 72
mep. at µ est. <0.01 M
Magnesium
1. MgO 12.4 ± 0.3 Optical grade MgO (Magnovite, Norton Robinson, Pask, and Fuerstenau 103
Co.) w, d, IEPS by sp
2. Mg(OH)2 (~12) un, ppt MgCl2 + NaOH, IEPS by mep. Mattson and Pugh 72
in µ est. <0.01 M
3. Mg(OH), (~12) un, IEPS by eo Michaelis 75
Manganese
1. Mn(OH)2 (7.0) un, ppt MnCl2 + NaOH, IEPS by mep. Mattson and Pugh 72
at µ est. <0.01 M
2. MnOj (4-4.5) Synth, ig. Mn(N02)2 in air, c (HNOj), w, Rao 98
d (160°) mole ratio O/Mn «* 2.06,
tetrag. Mn02 (x), IEPS by drift
Mercury
HgO 7.3 ± 0.3 ppt Hg(NO,), + NaOH, x, w, IEPS by Holmes 86
mep.
Nickel
1. NiO 10.3 ± 0.4 Baker and Adamson reagent, NiO, IEPS Holmes 86
by mep.
2. Ni(OH)2 11.1 db 0.4 ppt Ni(NOj)2 + NaOH, w, x, IEPS by Holmes 86
mep.
3. Ni(OH)s (~12) un, ppt NiCl2 + NaOH, IEPS by mep. Mattson and Pugh 72
in µ est. = 0.01 M
Platinum
PtO? (>14) Supposed oxide film on Pt in 1 atm. 02, Kruyt 83b
IEPS est. from pH dependence of Pt-02
electrode.
Plutonium
1. Pu02 9.0 Sulfate ig. (850°), IEPS by mep. Sowden and Francis 118
2. Pu02 8.6-8.9 Oxalate ig. (500-900°), ground, IEPS by Sowden and Francis 118
mep.
Silicon
1. SiO, 2.2 Natural a-Si02 (quartz)) See Table IV
2. Si02 (hydrous) 1.8 Si02 sols and gels )
Thorium
1. Th02 9.0-9.3 ppt oxalate from nitrate at room temp, to Sowden and Francis 118
70°, ig. (900-1100°), grind, IEPS by
mep.
2. Th02 (8.5-11) un, ppt Th(NOj)j + NaOH, w, d (100°), Amphlett, MacDonald, and 3
IEPS est. ads. (Na+, Cl") Redman
3. Th02 ppt oxalate from nitrate, ig. (20 hr. at Anderson 6
400° then 70 hr. at 900°), store C02
free, IEPS by mep. in µ indie.
(9.5) µ = 10 ~4 M KC1, uncertain only because
IEPS est. by scaling figure
(8) µ = 10-3 M KC1
(4.2) µ = 10~2 M KC1
4. Th02 (6.85) un, ppt Th(N08)4 + NaOH, IEPS by Mattson and Pugh 72
mep. in est. µ ~ 0.04 M
Tin
1. SnO (hydrous) (6.6) un, ppt SnCl2 + NaOH, IEPS by mep. Mattson and Pugh 72
2. Sn02 7.3 Mineral cassiterite, c, w, d (120°), IEPS Johansen and Buchanan 56
by mep.
3. Sn02 synth. HNOj + Sn(metal) 80°, Johansen and Buchanan 56
product w
Isoelectric Points of Solid Oxides and Hydroxides 181
Table I (Continued,)
Material IEPS Comment Investigator Ref.
SnOz (hydrous) 4.5 IEPS by mep., material as descr.
SnOz 5.5 SnOz(hyd) ig. (850°, 2 hr. in air), IEPS by
mep.
4. SnOz (8.5) Mineral cassiterite, c, w, d (120°), IEPS Johansen and Buchanan 55
by sp
5. SnOz Three natural cassiterites g, w, d (110°), O’Connor and Buchanan 79
IEPS by sp
4.7 74.6% Sn, low Fe
(9.5) 75.8% Sn, high Fe, “soluble base” present
4.7 75.4% Sn, low Fe
6. SnOz (hydrous) (3.9) un, ppt SnCh + NaOH, IEPS by mep. in Mattson and Pugh 72
est. µ ~ 0.01 M
Titanium
1. TiOz (3.5),4.7 Natural rutile )
See detailed citations in Table V
2. TiOz 4.7, 6.2 Synthetic rutile, anatase \
Tungsten
1. WOs (hydrous) (0.5) ppt NazW04 + HC1, IEPS by mep. El Wakkad and Rizk 27
2. WOs (hydrous) (<0.3) un, IEPS by eo Michaelis 75
Uranium
1. UOz-UsOs Samples synth. thermal decomp, ammo- Pravdic and Sotman 96
nium diuranate + Hz-HzO(g) mixt. at
temp, indie., ground, w, IEPS by sp.
5.8 ± 0.2 ig. (600°), cool in 3 hr., oxygen to uranium
mole ratio (O/U) 2.00, str. cubic by x
=
« Abbreviations:
ads., IEPS estimated as pH at which adsorption of indifferent positive ions equals that of negative ions (48, 83a)
a, aged or stored in distilled water for period indicated (if known); c, sample cleaned by leaching in concentrated HC1 or other acid
indicated; co, IEPS estimated as pH of maximum rate of coagulation of a suspensoid (129); d, sample dried <100° or as indicated,
stored dry; di, sample cleaned by dialysis; drift, IEPS estimated as pH at which suspension pH does not drift from that at which it
was made. Usually oxide is precipitated at initial pH of test (83a); eo, electroendoosomosis or electroosmosis (83a); ig., sample ignited
at temperature indicated; un, exact identification of solid missing. Structure or composition inferred from author’s statement or
sample history; mep., microelectrophoresis (1, 83a); ppt, sample prepared by precipitation using solutions of salts indicated; sp, IEPS
estimated as pH of zero streaming potential or current; sub, IEPS estimated as pH of maximum subsidence rate of a coagulated sus-
pension (129); ti, IEPS estimated as pH at which adsorption of H+ is equal to that of OH- as determined by potentiometric titration
of a suspension; µ, total salt concentration during IEPS measurement; w, sample washed in water, usually by decantation, until free
of Cl- or S042-, etc.; x, sample identified by X-ray diffraction; ( ), citations in parentheses are estimates based on insufficient or in-
adequately reported data or reports of experiments using poorly characterized solids. Unless otherwise noted, the only foreign ions
¡>
present in the systems reported are either Na+ or K+ and Cl-, NOs-, or C104-.
182 George A. Parks
Table II
Isoelectric Points of Aluminum Oxides and Hydroxides"
ieps Description Investigator Ref.
cx-AlíOs
1. 9.1-9.2 Synth. a-Al(OH)j ig. (1000-1350°), x, w, di, a (>2 days, 0.1 M Koz’mina, Belova, and Sannikov 63
KC1), w, IEPS by sp in µ = 10 "3 M KC1
2. -AlíOs, Linde A abrasive (Linde Air Products Co.) Robinson, Pask, and Fuerstenau 103
6.4-6.7 ig. (600-1400°), a (<1 day)
9.1-9.5 All non-ig. and ig. (<1000°) samples after a (H20, 7 days), x, c,
w, IEPS by sp, µ < "2 M KC1
7.7 ig. (1400°), a (H20, 7 days), etc.
3. Same basic material as 2 Yopps and Fuerstenau 129
9.1 x, c, w, a (7 days), IEPS by ti, µ = -’- "1 M KC1
9.0-9.1 x, c, w, a (7 days), IEPS by sub, µ 10_a-10° M KC1
=
KCIO4 separately
4. 7.5-8.2 Flame-fused synthetic sapphire, ground in mullite ware, not Holmes 86
cleaned, a (< 1 day), x, IEPS by mep.
5. “Chromatographic A1203 used as received” Herczyúska and Prószyúska 48
10 IEPS by ads. H+, CH-
9.8 ± 0.2 IEFS by drift
6. 6.7 Synthetic sapphire, c, w, d (120°), IEPS by eo Dobiá¿í, Spurn#·, and Freudlová 24
7. Natural corundum, c, w, d (120°) Johansen and Buchanan 56
8.4 IEPS by mep.
9.4 0.94% Si02, IEPS by sp Johansen and Buchanan 55
8. (9.4) Flame-fusion sapphire (Linde Air Products Co.), c, w, a, Modi and Fuerstenau 76
IEPS by sp
9. Schuylenborgh and Sanger 112
a. 2.3 Synthetic corundum
b. 3.0 Natural corundum, x, c, w, di, d, IEPS by mep.
7-Al203
1. 7.4-8.6 Synth. a-Al(OH)3, ig. (300-800°), x, w, di, a (>2 days, 0.1 M Koz’mina, Belova, and Sannikov 63
KC1), w, IEPS by sp in µ = 0.001 M KC1
2. (8.0) 7“A1203 prepared by thermal treatment and aging of the hy- Fricke and Keefer 31
drolysis product of A1 ethylate, IEPS by mep.
- (Boehmite)
1. 7.7 Synth. Al(OH)3 ig. (300°), di, a (>2 days in 0.1 M KC1), w, Koz’mina, Belova, and Sannikov 63
IEPS by sp in µ = 0.001 M KC1, x
2. (<2) Natural bauxite, x, di, d, IEPS by mep. Schuylenborgh and Sanger 112
3. Synthetic - , x, w, di, d, IEPS by mep. Schuylenborgh 111
8.8 Synth, from A1C18 + NH4OH at 18°
6.5 (ci), 7.6(c) Synth, from Na3A103 (ci and c2 = 100ci) + C02
4. 9.4 Synthetic boehmite, prepared by thermal treatment and aging Fricke and Keefer 31
of the hydrolysis product of purified A1 ethylate, IEPS
by mep.
7-A100H (Diaspore)
1. (<2) Natural diaspore, x, di, d, IEPS by mep. Schuylenborgh and Sanger 112
2. Synthetic diaspore, x, di, d, IEPS by mep. Schuylenborgh 111
7.5 Synth, at 70° from A1C13 + NH4OB, product - + tr
7-Al(OH)3
5.4 Synth, from Na3A103 + C02(g)
a-Al(OH)3 (Gibbsite, Hydrargillite)
1. 3.8-5.0 Synth. a-Al(OH)3 (3.8) and same ig. (200°) (5.0), di, a (>2 days Koz’mina, Belova, and Sannikov 63
in 0.1 M KC1), x, w, IEPS by sp
2. 5.0, 5.2 Natural gibbsite (two samples), di, d, IEPS by mep. Schuylenborgh and Sanger 112
3. 4.9 Synth, by aging Na3A103(aq), di, d, x, IEPS by mep. Schuylenborgh 111
7-Al(OH)3 (Bayerite)
1. 9.3 ± 0.2 7-Al(OH)3, synth. by hydrolysis of purified Al(OC2Hs)3, x, w, a, Korpi and Holmes 86
IEPS by mep.
2. Synthetic materials, x, w, di, d, IEPS by mep. Schuylenborgh 111
7.5 Synth, from A1C13 + NH40H(aq) at 70°
5.4 Synth, from NasA103(aq) + C02(g)
3. 9.2 7-Al(OH)3 synth. by hydrolysis of purified Al(OC2H3)3 or re- Fricke and Keefer 31
lated compounds, IEPS by mep.
Isoelectric Points of Solid Oxides and Hydroxides 183
Table II (Continued)
IEPS Description Investigator Ref.
In buffers IEPS shifts as follows: glycocoll (9.00), borate (6.78), Fricke and Leonh&rdt 32
acetate (5.59), phosphate (4.05), citrate (2.4). Buffer con-
centrations not given
Amorphous A1203
1. ppt A1C1» (aq) +
NaOH as descibed, IEPS by mep., IEPS given Tewari and Ghosh 120
in parentheses. If 10% excess NaOH; w (5.08), a (4 mo.
room temp.) (5.78); a (temp. > room temp.) (6.79); if
stoichio. NaOH, w (6.63), a (4 mo., room temp.) (7.06); a
(temp. > room temp.) (7.28); if 10% deficient NaOH, w
(7.29), a (4 mo., room temp.) (7.32); a (temp. > room temp.)
(7.43)
2. 8.0 Unaged product of hydrolysis of very pure aluminum ethylate, Fricke and Keefer 31
IEPS by mep.
3. ppt from AlCls or A12(S04)3 with NaOH adjusted to fix final pH. Mattson 71
IEPS by mep. without washing (see text)
8.0 ± 0.2 In solid, mole ratio Cl/Al2Oa ca. 0.005
7.5 ± 0.2 In solid, mole ratio S04/A1203 co. 0.074
•
For meaning of abbreviations see footnotes, Table I.
Table III
Isoelectric Points of Iron(III) Oxides and Hydroxides'*
IEPS Description Investigator Ref.
Natural a-Fe203 (Hematite)
1. Hematite Joy, Watson, and Cropton 58
5.7 IEPS by sp
5.4 IEPS by ti
2. (4.5-5.0) c, w, a, IEPS by ti and suspension effect (83a) Chwastiak 20
3. 6.6 ± 0.2 Specular hematite (Labrador),6 c, then ground in mullite Holmes and Feeney 86
ware, w, a, IEPS by mep., two independent observations:
6.6, 6.7
4. 6.7 ± 0.1 Mineral selected, ground, w, IEPS by mep. Iwasaki, Cooke, and Choi 51
5. 6.9 ± 0.2 Same sample described under 3,6·" c, w, a, IEPS by sp, µ =
Korpi 59
"4 M KN03
6. (4.2) Mineral c, w, d (120°), IEPS est. from sp data Johansen and Buchanan 55
7. 6.7 Mineral c, w, d (120°), IEPS by mep. Johansen and Buchanan 56
8. (2.2) Mineral x, c, w, di, d, IEPS by mep. Schuylenborgh and Sanger 112
Synthetic <*-Fe203
1. All materials synth. by 100° hydrolysis and aging under
reflux conditions of Fe(N03)3 solution, w, a, x, IEPS by ti
(H+, OH-) unless otherwise noted
a. 8.7 ± 0.1 µ < 1.0 M, 4 determinations, once each in NaNOs, NaCl, Albrethson 2
NaClOj, Na2S04, 25°
8.85 ± 0.2 0.005 M NaNOs, IEPS by suspension effect (83a)
b. 9.04 ± 0.05 µ =
0.001-0.10 M KNOs, 25° Korpi 59
c. 9.03 ± 0.05 µ < 0.01 Af KNOs, 21° Parks and de Bruyn 85,
8.77 µ =
1.0 M KNOs, 21°
8.7 ± 0.2 µ =
0.01-0.10 M KNOs, 38°
2. Baker and Adamson reagent grade* Fe203 (synth. by ignition
of Fe(S04)3 in air or 02), w, a, x
8.4 ± 0.1 IEPS by ti at 21°, µ < 0.1 M KNOs Parks 85
8.0 ± 0.2 IEPS by mep. Miaw 74
3. Starting materials synth. FeNH4(S04)2 + NH4OH, w (5% Johansen and Buchanan 56
NH4N03), w, IEPS by mep.
8.0 ppt as described
6.5 ppt, d, ig. (850°, 2 hr.)
4. 1.9 Synth, x, w, di, d (105°), IEPS by mep. Schuylenborgh and Sanger 112
5. 8.3 Fe203 sol synth. FeCl3 + NH4OH, w, a (H20, 150-160° at Toelstra and Kruyt 121
*~5 atm.), IEPS by mep.
7-Fe203
1. 6.7 ± 0.2 Synth, by ppt FeOOH, ig. to Fe2Ol, x (tr. 7-FeOOH), w, Iwasaki, Cooke, and Kim 54
IEPS by mep.
184 George A. Parks
1. (7) “Hydroxide” IEPS est. by ads. (Zn2+, Co2+) Zhabrova and Egorov 131
2. Synth. Fe(NO,)3 + NH4OH, IEPS by mep. Schuylenborg, Arens, and Kok 110,113
8.5 w, di, not dried
6.0 w, di, d (60°)
4.3 w, di, d (105°)
3. 8.6 FeA sol by hydrolysis FeCl3, di (5 days, 90°), a, IEPS Hazel and Ayres 47
by mep.
4. ppt from FeCls or Fe2(S04)3 with NaOH adjusted to fix pH, Mattson 72
IEPS by mep. without washing (see text)
7.2 Mole ratio Cl/FeA in solid is 0.005
7.0 Mole ratio S04/FeA in solid is 0.014
5. (8.8 ± 0.5) IEPS by eo Michaelis 75
See footnotes, Table I, for abbreviations. » 99.77% FeA, 0.05% FeO, 0.09% Si02, same material used by Korpi (59). c Washed
<*
in hot alcoholic , hot H20, HNOs in Soxhlet extractor for 3 hr., H20 in Soxhlet for 3 days, stored in dist. H20. d <0.2% insol.,
<0.2% SOi2", <0.005% Cu, Zn. · 2.4% Si02, 1.7% A1A, 1.3% P206 (30). / 58.73% Fe, 2% Si02, 0.46% Mn, 10.25% H20 (400°),
11.24% H20 (800°). 8 56.62% Fe, 10.5% H20, 0.93% insol.
Table IV
Isoelectric Points of Si(V
IEPS Description Investigator Ref.
-SiOí (Quartz)
1. 1.5 Brazilian crystal, ground, c (HC1 in Soxhlet extractor), w (8 hr., H20 Bhappu 10
in Soxhlet), a, IEPS by mep.
1.8 Crystals from Harding Mine, N. M., ground c, w, a, IEPS by mep. Bhappu 10
2. 2.5 ± 0.2 Natural crystals (Mont.), c, w, a, IEPS by mep. Iwasaki, Cooke, and Choi 53
3. 2.2-2.8 Quartz from a beach sand (E. H. Sargent Co.), c, w, a, IEPS by sp, Flaningham 30
IEPS 2.8 after ample aging at test pH (<2 days)
=
Table V
Isoelectric Points of Ti02“
IEPS Description Investigator Ref.
Natural Ti02 (Rutile)
1. 4.7 ± 0.2 Sample from N. C., ground, w, x (tr Fe203), IEPS by mep. Feeney 86
2. 3.5 ± 0.2 c (H2S04, HC1), w, IEPS by sp Graham and Madeley 44
3. 4.8 c (HC1), w, d (120°), IEPS by mep. Johansen and Buchanan 56
4. 5.5 c, w, d (120°), IEPS by sp Johansen and Buchanan 55
Synthetic Ti02
1. 6.7 ± 0.1 High purity synthetic rutile (National Lead Co.) c (HC1 in Soxhlet extractor), Purcell and Sun 97
w (8 hr., H20 in Soxhlet), a (H20), IEPS by sp in µ < 10-! M NaCl
2. 6.0 ± 0.3 Average observed by two operators for several samples including reagent grade Feeney and Holmes 86
Ti02 (anatase), Ti02 (hydrous rutile), x, s, w, a, IEPS by mep.
3. Samples synth. hydrolysis TiCl4 at 100° hydrous rutile, w, a, IEPS by mep. Johansen and Buchanan 56
6.0 As described
4.7 d, ig. (1000° in air, 2 hr.)
4. (4.8) un, synth. TiCl4 + NaOH, IEPS by mep. in µ est. 0.02 M (see text) Mattson and Pugh 72
<*
See footnotes, Table I, for abbreviations.
sorption for, e.g., Si02 (14), and by total reaction for bond strength which must accompany an increase in
MgO (102) and decreases the solubility. Mechanical m/n (89). The original articles should be consulted for
disturbance, e.g., by grinding, leads to an amorphous or details.
disturbed layer with increased solubility, e.g., Si02
(122), and increased surface hydration, e.g., A1203 (55).
S. Effects of Impurities
If oxide precipitates form by progressive hydrolysis, Purposeful investigations of the effects of impurities
polymerization, and oxolation (104, 126), it can be ex- on the IEPS are few. Because many systems in which
pected that they would retain a superficial layer of more the IEPS is studied provide ample opportunity for
hydrous material which would be lost only on drying contamination by adsorption or reaction, the subject is
and ignition. While it is well established that very quite important. Abramson, Moyer, and Gorin (1)
high temperatures are needed to remove the last MOH pointed out that the “real” IEPS could be measured
groups from silica gels and that persistent MOH groups only in the absence of all ions other than hydrogen,
are present in other oxides (130), direct evidence of hydroxyl, and those which are components of the solid.
persistent hydrous films is lacking in most cases; how- In discussing the origin of charge on organic colloids
ever, there is at least some evidence for the presence of they listed the following charging processes: (1) dis-
hydrous films on Fe203 (86, 87) and Zr02 (21) prepared sociation, particularly acid-base dissociation of surface
by hydrolysis. For Fe203, the solid was identified as groups such as -COOH, -SiOH; (2) specific adsorp-
hematite by X-ray diffraction, yet DTA and infrared tion of ions onto otherwise neutral sites (tendencies
absorption experiments yielded evidence for traces of toward ion-pair formation, hydrogen bonding, and
FeOOH (86). “specific interactions” such as are responsible for com-
Detailed study of sample preparation for the Al(III) plex formation in solution were mentioned as possible
and Fe(III) materials for which IEPS data are summa- “driving forces” for specific adsorption); (3) ori-
rized in Table I makes possible several generalizations. ented adsorption of polar molecules such as H20 with
All of the oxides and hydrous oxides of aluminum subsequent adsorption of ions by 1 or 2 above; (4)
apparently slowly hydrate (in a matter of days) to the weak specific adsorption of ions by induced polariza-
extent that at least a film of material with the properties tion of the substrate (image force bonding).
of 1( )3 results. Amorphous Al(OH)3 has the same Mechanisms 2-4 may be called specific adsorption,
characteristics as the crystalline modifications. The using the term in the sense used by Grahame (45) to
IEPS characteristic of - 1203 at equilibrium with water denote any tendency toward interaction other than the
is probably about pH 9.2. All other values presently simplest electrostatic case. It is assumed that perchlo-
available for this material seem to represent metastable rate, nitrate, and chloride ions do not interact with oxide
or impure states. surfaces in any specific sense and that the charging
Ignited and natural Fe203 samples appear to hydrate process characteristic of oxides in aqueous suspension
quickly to the extent that their surfaces have the prop- is either acid-base dissociation or specific adsorption of
erties of -FeOOH. The more basic IEPS of -FeOOH metal hydroxo complexes. The effects of other ions
can probably be attributed to the effect of the less stable will be classified impurity effects.
as
structure. a-Fe203 hydrates no further in reasonable Overbeek (83c) has pointed out that specific adsorp-
time. a-Fe203 prepared by hydrolysis and not sub- tion of anions would be expected to produce a negative
sequently dried at high temperature has the IEPS of surface charge under conditions otherwise identical with
hydrous or amorphous Fe203 and apparently retains a the IEPS. Should this occur on an oxide surface, the
coating or film of hydrous material as predicted above. pH at which zero surface charge was observed would be
Fe203 with IEPS near pH 5 apparently remains hy- lowered; i.e., the apparent IEPS would be shifted to a
drated to a lesser extent than FeOOH, perhaps only more acid pH because increased H+ adsorption would
physically adsorbing water. be necessary to neutralize the anion’s negative charge.
The change in IEPS accompanying changes in hydra- A structural anionic impurity would be expected to
tion has been interpreted in terms of the dependence of produce an acid shift as well because the M-anion-H
the acid strength of surface MOH groups on the O2-/ surface group would in most cases be a stronger acid
OH- ratio by O’Connor, Johansen, and Buchanan (80) than -MOH.
and by Robinson, Pask, and Fuerstenau (103). Similar Both adsorbed and structural cationic impurities
arguments have been used to interpret the strengths of present before measurement of the IEPS would be ex-
the oxyacids, MOm(OH)„ (77, 89). In the latter case pected to shift the IEPS in the direction of the IEPS of
an increase in the ratio, m/n, is said to result in an the impurity hydroxide. Extensive evidence has been
effective increase in Z/r, the ratio of cationic charge to given (26) for cation adsorption on silica gel by ion
radius, and consequently in acid strength. Increased exchange with H+ from -SiOH sites. In addition to an
acid strength (or decreased IEPS) could equally well be IEPS shift in the direction of the appropriate oxide,
explained in terms of the increased electrostatic slight nonequivalence of MI+/H+ exchange would also
Isoelectric Points of Solid Oxides and Hydroxides 187
Table VII
Effects Impurities on IEPS
of
A. Structural Impurities (Present in Solid before Experiments)
Substrate Impurity Impurity level, mole % 80 Ref.
A1203 (hydrous) so42- ~7.4 >-0.5 72
ci- ~0.5 .—0 72
Fe202 (hydrous) SÜ42- ~1.4 -1.6 72
Fe20« (anhydrous) sc>42- ~0.3 —0.2 to —0.6 74, 85
Fe202 (hydrous) Cl- ~0.5 <-1.4 72
Si02 (ignited gel) A1203 (coprecip.) Var., <40% A1203 = 0.12 (mole %
A1203) 56
Sn02 (mineral) Fe203 + “soluble base” Unknown <+4.7 79
B. Adsorbed Impurities (Present in Electrolyte before_Experiments)
Substrate Impurity Impurity level, M AIEPSa Ref.
A1203 h2po4- ~5 X "3 ~ —4 21
A120$ SOt2- ~3 X 10 "4 -2.9 76
ThOt ci- ~10-3 -1.2 6
Th02 Cl- ~io-2 -5.0 6
Ti02 SÜ42- ~10"3 -0.7 97
T1O2 Ca2+ ~10-4 +0.3 97
> 10-4 >+4.8 97
«-FeOOH La3+ 10-8» + 1.4 30
a-FeOOH La2+ 10-4 6 +2.0 30
a-AljOj Na dodecyl sulfate ~3 X *6 Est. —5.4 76
CX-AI2O3 Na cetyl sulfate ~2 X '6 Est. —2 79
a-Fe203 Dodecylamine 2 X "6 +0.05 58
a-F^Os Dodecylamine 6 X '5 +0.10 58
a-Fe203 Dodecylamine 10 X "6 +0.25 58
a-Si02 DTAB' 2 X ”6 Est. +5 81
d i Est. +4.5 ± ~1.5) 36
a-Si02
a-Sn02 Na cetyl sulfate 2 X "3 Est. —0.7 79
<x-Ti02 (rutile) Na oleate ~10-8 -3.7 97
*
8 > 0 indicates basic shift of IEPS. 6 FeOOH equilibrated with La(N03)3 solution then rinsed once before mep. ' DTAB =
dodecyltrimethylammonium bromide. d Each of the alkylamine acetates, Cs (~10_1 M), Cm (~3 X 10-3 M), Ci2 (3 X 10-4 M), Cu
(~10-4 M), and Ci« (2 X 10-s M) give the indicated 8.
be expected to produce a shift by the same mechanism same The IEPS shifts acid as the oxidation
source.
discussed for anions; i.e., should the equivalents of H+ as would be predicted from the change
state increases,
lost exceed the equivalents of Mz+ adsorbed, the IEPS in Z/r ratio. The points marked “calculated” in
would shift to a more acid pH. Figure 2 were obtained using Eq. 2c to be developed
The effects of various structural or adsorbed impuri- below.
ties on the IEPS’s of several oxides are summarized in It might be expected that simple heat treatment of
Table VII. The expected shifts are observed. some oxides, such as Ti02, Sn02, and Mn02, would re-
Specific adsorption of dissociable species exceeding a sult in superficial loss of oxygen and, consequently, non-
monolayer can be expected to shift the IEPS to or stoichiometry. This has been observed for Ti02 (34)
toward that of the adsorbate. The best example is the and interpreted as production of Ti203 in the surface.
adsorption of proteins (1, 12) which shifts the IEPS A shift of IEPS in the direction appropriate for the
completely to that characteristic of the adsorbate in oxidation state produced would be expected quite apart
each case. from dehydration effects because the average Z/r
changes. There is at present very little evidence in
4· Nonstoichiometry, Defect Structures, support of this point. However, a preliminary attempt
and Semiconductors
(86) gave the following results which do show the correct
Pravdic and Sotman (96) reported the only work trend.
that has been done on variation of IEPS with reason-
Precipitated Ti02 (hydrous rutile) IEPS = 6.0 ± 0.3
ably well-defined deviations from stoichiometry. The Ppt. heated to 975°, 2 hr. IEPS = 6.3 ± 0.2
variation of IEPS with the mole ratio of oxygen to Ppt. heated in 10% H2, 975°, 0.5 hr. IEPS = 6.3 ± 0.5
Ppt. heated in 10% H2, 975°, 2 hr. IEPS = 7.4 ± 0.2
uranium (O/U) in the series U02-U30s is shown in
Figure 1. The data of Parreira and Ottewill (88) with The loss of oxygen and IEPS shift could be explained
natural pitchblende (intermediate between U02 and equally well by assuming that oxygen vacancies and
U3Os) have been plotted on the same figure using an n-type semiconductivity result from heat treatment.
O/U ratio ( 2.3) reported (84) for material from the
=
An n-type semiconductor would be expected to exhibit
188 George A. Parks
8
been taken of the postulated analogous dissociation
behavior of surface -MOH groups and dissolved molec-
ular hydroxides and oxyacids. Kossiakoff and Harker
6 (62, 77) found it possible to quantitatively account for
O
the strength of oxyacids using a purely electrostatic
e model of the acid dissociation process. The important
o variables are the formal charge of the cation, the num-
° ber of nonhydroxyl oxygen ions (m/n or the hydration
state), and the geometrical arrangement of the ions (77).
+2 A similar but less thoroughly developed analysis based
on the amphoteric dissociation model for the origin of
surface charge has been found useful. Equilibrium
0 between positive and negative surface sites involving
O 2H+, i.e.
MO-(surf) + 2H+ MOH2+(surf) =
-2
is assumed to involve primarily the electrostatic work
Porreira and Ottewill (88)
gained by the approach of 2H+ to MO-. As a first
O Pravdic and Sotman (96)
approximation, each ion (the two hydrogen ions are
Calculated
treated as a doubly positive entity) is assumed a point
2.0 2.2
J-1_I_I_L
2
charge separated from the others by average oxide ionic
2,6 2.8 3,0
o/u
radii (46) (the radius of O2- is taken as 1.40 A.) in a
linear array. The free energy involved is then (9a, 62)
Figure 1.—The effect of composition on the IEPS of uranium
oxides. -2ZBZ0(e-)* , 2ZHZ+(e-)* .
a more basic IEPS than predicted for the stoichiometric «(ro) +"«(2r0+r+) +
AF' =
RT In K (Eq. 1)
oxide owing to stabilization of adsorbed H+ by mobile
electrons. Similarly p-type semiconductors might be or, since
B{Z/R) -
DAF' (Eq. 2)
been studied to any significant extent.
The hydrous oxides precipitated from metal salt where AF' = non-Coulombic contributions to the hy-
solution are defect structures containing a high con- drogen ion binding energy; , , =
constants; Z
centration of structural defects and excess H20 in addi- = ionic charge of species indicated by subscript =
tion to coprecipitated ions (124). Schuylenborgh, H+, 2-, + cation; e appropriate dielectric
= = =
Arens, and Sanger (110-113) in a painstaking study of constant of water; e- electronic charge; r = =
aluminum and iron oxides and hydroxides were able to ionic radius, R 2ro + r+; ()
=
ionic concentration =
show that any feature of sample history leading to in- or activity. Equation 2 predicts that the IEPS should
creased crystal perfection (observed by X-ray diffrac- vary linearly with Z/R, increasing as Z/R decreases.
tion line narrowing) leads to decreased IEPS. As dis- The prediction is roughly verified in Figure 2, a plot of
cussed under “Effects of Hydration,” substitution of IEPS vs. Z/R.
H20 for O2- or OH- would be expected to shift the Such a simple electrostatic model cannot apply ac-
IEPS to a more basic pH. A cation vacancy should curately for several reasons: (1) Crystal field effects
have the same effect because hydrogen ions would be increase the stability of the M-OH bond (9b), decreas-
accepted to make up the charge deficiency resulting in ing the IEPS by reducing the basicity of the group.
an increased effective 0H-/02- ratio. Presumably, The crystal field stabilization energy (CFSE) contributes
aging results in loss of excess molecular H20 and com- to the term AF’ in Eq. 1. (2) The contributions of
bination of substitutional H+ with excess OH- to form additional coordinating anions constitute a different
H20 which is subsequently lost (122, 124) resulting in constant term for each coordination number. (3)
the acid shift of IEPS observed. The value of A in Eq. 2 is different for each value of the
ratio m/n of nonhydroxyl to hydroxyl oxygens. The
C. VARIATION OF IEPS WITH CATIONIC
exact hydration state of solids for which lEPS’s are
SIZE AND CHARGE available is usually not known; hence, it is possible
1. An Electrostatic Model only to consider two extremes, hydrous and anhydrous,
In examining the IEPS data to detect expected using the term “hydrous” in the generic sense described
trends with cationic size and charge, advantage has earlier.
Isoelectric Points of Solid Oxides and Hydroxides 189
It is feasible to account for these effects analytically, nated wdth OH- rather than H20 (9b,d). Hence the
but this refinement is unwarranted at present. In- relative magnitudes of CFSE should be the same in
stead, the constants A and B of Eq. 2 will be evaluated the hydroxides as in the hexaaquo ions. We will
separately for each coordination number and hydration assume that the crystal field contribution to the
extreme, and the CFSE correction will be evaluated for OH binding energy in the hydroxides and hydrous
each transition metal ion by analogy wdth calculations oxides, etc., is proportional to that calculated for the
of simple electrostatic and CFSE terms in the hydration hexaaquo ions. The appropriate energies, scaled from
energies of these ions. figures in Basolo and Pearson (9c), are listed in Table
VIII.
2. Coordination Number Six and Equation 2 may be rewritten to take the CFSE into
Crystal Field Effects account as
B{Z/R) -
(Eq. 2b) .
the line, indicating that the equation is valid over 12 wras then used to calculate (Z/R)eit for the other transi-
orders of magnitude in H+ concentration. tion metals, in some cases making possible predicted
As expected, the IEPS’s of the transition metal values where no measurements are available. The
hydroxides are not described by Eq. 2 in this form. results are summarized in Table VIII. The validity of
The crystal field contributions to the hydration energies this approach is amply demonstrated by comparison of
of these ions have been calculated (9b,c). The CFSE columns 6 and 7 in Table VIII and study of Figure 2.
in the hexaaquo ions corresponds to a weak crystal In Figure 2, plotting IEPS against (Z/R)e¡t brings the
field. The field is still weaker if the cation is coordi- points for all the hydrous transition metal oxides or
190 George A. Parks
Table VIII
Crystal Field Corrections to (Z/R)eti
Approx. CFSE Predicted IEPS' Measured
for M'+(HiO)«, for hydroxide or IEPS (hydrous
Ion kcal. (9c) ( / )« Z/R (46) (Z/R)sif hydrous oxide
materials)
Mn!+ 0 0 0.54 0.54 12.4
Mn3 + 42 0.12 0.79 0.91 8.1
Fe2+ 18 0.05 0.54 0.59 11.8 12
Fe3+ 0 0 0.81 0.81 9.3 8.6*
Co2+ 33 0.10 0.54 0.64 11.2 11.4
Co3+ 42 0.12 (O.SIP (0.93) 7.9
Nia+ 42 0.12 0.54 0.66 [11.0]/ [11.1]
Ni3+ (30) 0.09 (0.81) (0.90) 8.6
Cu2+ 39 0.11 0.53 0.64 11.2 9.4
Sc3+ 0 0 0.77 0.77 11.2
Cr2+ 72 0.20 (0.50) (0.70) 10.6
Cr3+ 70 0.20 0.80 1.00 7.1 7.0
y2+ 73 0.21 (0.54) 0.75 10.0
ys+ 39 0.11 0.78 0.89 8.4
Ti2+ 68 0.19 (0.53) (0.72) 10.3
Ti>+ 30 0.09 0.78 0.87 8.6
«
AiZ/R) 0.0029(CFSE). * (Z/R)m =
=
Z/R + A(Z/R). - From Eq. 2b. d Entries in parentheses are estimates. ' -~9.0
Fe2Os from nitrate hydrolysis, see Table III.
* Entries in brackets were used to evaluate constants in
Eq. 2b.
hydroxides except that for Cu(OH)2 onto the line rep- = 6. Inasmuch as the description of these materials
resenting Eq. 2a. indicates that U02 and Zr02 should be classed among
While the coordination number (CN) of Cu(II) in the “anhydrous” materials, the assignment of a value to A
hydroxide has been assumed to be six in accord with the for this entire group must remain tentative.
structures of several oxyhalides (125b), the hydroxide is
Summary 5.
unstable relative to the oxide in which Cu(II) is found
in square-planar oxygen coordination (125b). The In order to make possible a convenient graphical test
CFSE for Cu(II) in square-planar coordination should of the validity of Eq. 1 and 2 they can be expressed in
be larger than has been used for octahedral coordina- the alternate forms
tion (9c), hence the failure of this one point to correlate IEPS =
Aeff -
11.5\Z/R + 0.0029(CFSE)] (Eq. 2c)
with (Z/R)eti can be understood.
We have seen that oxide IEPS’s are more acidic than and
the corresponding hydroxides or hydrous materials. A IEPS = 18.6 -
11.5\Z/R + 0.0029(CFSE) + o]
straight line of slope 11.5 can be fitted to the points or
representing oxides with CN 6. Its intercept, A =
=
Figure 3.—The relationship between IEPS and {Z/R)<>it, illustrating corrections for crystal field effects, coordination, and hydration.
Table IX
Correlation Constants Aeí¡ and a
hydroxides, hy-
drous oxides, su- a = 0.21 a = 0.0
perficially hy-
drated or hydrous
oxides
“Anhydrous” ox- Aeff =14.1 Aeff = 16.5 A = 20.7
ides a = 0.39 a = 0.18 a =
-0.18
species are small, is usually essentially equal to the The relationships among the IEP’s and the various
IEP. The pH of minimum solubility, the pHMS, is EP’s are illustrated in Figure 4 where the concentra-
identical with the IEP. The EP(4,1) is the pH at tions of mononuclear hydroxo complexes in equilibrium
192 George A. Parks
In other columns the meaning of multiple entries is the Nondissociative or physical adsorption involves no dis-
same unless indicated otherwise. sociation of surface -MOH groups and is assumed to be
governed by equilibrium constants nearly equal to those
IV. Comparison of the Isoelectric Points of for adsorption of hydroxo complexes and the same for
Solids with Those of Hydroxo Complex Systems H+ and OH-. The adsorption reactions can be repre-
sented by
A. GENERAL OBSERVATIONS
-MOH + H+ — -MOH·· · +
The IEPS’s are compared with corresponding IEP’s -MOH + OH- -* -MOH- -OH- ·
in Figure 5. It is obvious that the two quantities are The IEPS is thus equal to the IEP if the PDI, as
related, especially for the hydrous oxides and hydrox- determined by relative concentrations, is any pair
ides; however, detailed comparison of each IEPS and
among H+, OH-, Mz+(OH)z_i+, and Mz+(OH)z+i-,
all of the corresponding EP’s immediately reveals that
in many cases the IEPS is more closely approximated provided H+ and OH- adsorb dissociatively. The
equivalence of H+ and Mz+(OH)z_i+ as PDI arises
by an EP other than the IEP. Table XI lists the because development of a positive site by surface dis-
materials studied in groups according to the EP which
sociation or by formation in solution and subsequent
most closely matches the IEPS. Where several IEPS’s
are reported in Table I, the value selected for compari-
adsorption of a monopositive complex are indistinguish-
able processes.
son in Table XI is given in parentheses.
The near equality of IEPS and IEP for materials in
After study of the properties of the materials in each
column 1, Table XI, and the fact that for most systems
group several trends emerge: (a) all materials for
which IEPS IEP are hydrous and most have CN
= =
(OH-)> (M*+(OHUi-)
6 (those in this group with CN 9^ 6 have CN =
4 and and
r* < 1.0 A.); (b) with the exception of HgO, the (H+) < (M*+(OH)_i+)
Isoelectric Points of Solid Oxides and Hydroxides 193
Table X
Isoelectric Points and Equivalence Points for Several Hydroxo Complex Systems
IEP or EP(1,1) EP(2,1) EP(l,OH) EP(2,OH) EP(3,1) and others Ref.
Al(III)0 7.5 6.2 7.2 <*-AI(OH)3 and Al- 5.8 5.9 4, 8,13,17, 23
OOH 25, 29, 33, 42, 65
(6.2-7.7) 7.7 amorph 73, 94,105,107
Sb(III) 6-6.5 37, 93
Sb(V) 93
Be(II) 10.1 (6.6-7.9) 9.8 (inact.) 6.6 13, 29, 65
(9.9-10.4) 10.2 (act.) 7
Cd(II) 11.7 11.1 9.3 (act.) 9.4 (inact.) 13, 29, 41, 70, 128
(11.4-12.3) (10.8-11.3) 9.6 (act.)
Cr(III)6 8.4 8.1 8.2 7.8 6.5-7.0 13, 28, 29, 65
(8.2-9.3) (7.8-8.6)
Co(II)6.c 10.8 10.5 8.2 (pinkCo(OH)2 8.9 13, 29,116
(8.9-11.8) (7.8-11.3) 9.0 (blue) 9.4
Cu(II) 9.4 9.0 7.6 7.3(CuO) 13, 29, 65, 90, 128
(9.4-10.1) (8.9-9.3) 7.9 (Cu(OH)2)
Felll)" 12.4 10.8 9.9 (inact.) 9.1 13, 29, 40, 65
(11.3-12.4) (10.5-11.5) 10.4 (act.) 9.5
Fe(III)* 8.0 6.4 4.7 (a-FeOOH) 4.8-4.9 3.5 (a-Fe2Os) 11, 29, 40, 66, 109,
(7.4-8.4) (5.6-6.7) 5.7 (“act. Fe(OH)s”) 4.0 (a-FeOOH) 128
4.5 (“act. Fe(OH)3”)
Pb(II)/ 10.8 9.5 10.0 (red PbO) 8.9 13, 29, 65, 94, 128
(10.6-11.1) (9.4-9.8) 10.1 (yw PbO) 9.0
10.3 (Pb(OH)¡¡) 9.1
Mn(II) 11.8 11.3 9.6 9.7 13, 29
Hg(II) 8.6 7.1 (6.3-7.1) 5.6 13, 29
(8.4-9.4) (6.8-7.2)
( )» (0.9-1.5) 49, 95,115
Ni(II)1' 9.4 9.8 8.6 (act.) 8.4 13¡ 16, 29, 94, 95,
(7.9-10.3) (8.8-10.4) 7.4 (inact.) 9.2 116
Si(IV)* (2.8-3.2) EP(H,1) = 5.2-5.7 13, 14, 18
Ag(I) 12.1 29, 57
(12-12.2)
Sr(II)< 12.9 60
Te(IV)* (3.8-4.2) 50
Th(IV) ~11.2 ~8.9 ~7.8 -~6.4 13, 29, 38
Sn(II) 7.3 5.8 7.1 5.4 13, 22, 29, 35
(6.4-7.3) (5.2-5.8)
Ti(IV)* 6.6 5.6 —0.8 (rutile) 0.4 18, 29, 65, 69, 94
(6.6-7.1) (5.5-5.8) 4.7 (amorph.) 3.7
U(VI)1 (9.0-9.8) (7.3-7.8) (7.7-8.0) 6.7 13, 39, 43
V(V)s'm (1.0-2.5) 27,106
W( VI )''·’" (0.4-1.0) 27, 49
Zn(II)" 10.0 9.4 8.6 (ZnO) 8.5 (ZnO) 13, 29, 91, 92, 108
(8.7-10.6) (8.6-9.8) 9.5 (Zn(OH)2 amorph.) 9.0 (Zn( OH )2 amorph.)
Zr(IV)° (9.8-10.5) (7.2-7.6) 7.5 5.5 13, 29, 61, 65, 94
“
Several values of IEP are available as pHMS data estimated graphically. For 7-Al(OH)3, 7.7 (42); for “amorph. Al(OH)3,” 7.3
(73); for a-Al(OH)3, 6.3 (127); for “bauxite,” 7.2 (73); for -y-AlOOH, 6.5-7 (89); for a “hydrous oxide,” 7.2 (101). If surface struc-
ture changes from amorphous on acid side to boehmite on basic side, the IEP can be as basic as 8.4 (29, 73). 6 K,o (93); Ks K& (28, 1,
Table XII
Summary of Probable Potential-Determining Ions and Equivalence Point-Isoelectric Point
Relationships for Two Classes of Solids
Description of solid Hydroxo complexes present Hydroxo complexes absent
A. Hydroxides, oxyhydroxides, hydrous PDI are M,+(OH),_i or
+ + and PDI H+, CH-
are
oxides, and superficially hydrated or hy- '+( ),+ or CH- IEF =IEPS
drous oxides. CN = 6 and CN 4 if = (dissociative adsorption)
r+ < 1.0Á. IEF IEPS =
(dissociative adsorption)
P. “Anhydrous” oxides and class “A” PDI are same as class “A” and PDI are H+, OH
materials with CN = 4 and r+ > 1.0 Á. EP(+,OH) or EP (+, —) = IEPS IEPS pH 7
(nondissociative adsorption) (nondissociative adsorption)
Isoelectric Points of Solid Oxides and Hydroxides 195
Ti(IV) IEPS = 3.5 EP(2,OH) = 3.7 IEP = 6.6 V. Summary and Conclusions
Zr(IV) IEPS = 4.0 EP(2,OH) = 5.5 IEP = 10.2 Extensive lists of isoelectric points of solid oxide
Zr(IV) IEPS = 6.7 EP(2,1) =
(7.2-7.6) IEP = 10.2 materials (IEPS’s) and of metal hydroxo complex
systems (IEP’s) have been compiled. The IEPS
Of these, the IEPS’s of Al(III), Th(IV), and Zr(IV) reflects the chemical composition of the solid and the
also fail to correlate with (Z/R)ett This point and the electrolyte in which it is immersed. Structural or
coincidence that this particular IEPS = EP(2,OH) or adsorbed anionic impurities shift the IEPS to more
EP(2,1) do seem to indicate that a different mechanism acid values, cationic impurities to more basic values
is operating to establish equilibrium between the solid or toward the IEPS characteristic of the impurity oxide.
and the liquid in these cases. However, neither Oxidation and reduction resulting in nonstoichiometry
realistic justification for the fact nor physical reasoning may be expected to shift the IEPS toward that charac-
upon which to base selection of the exclusive potential- teristic of the oxidation state produced. Hydration
determining role of Mz+(OH)z_22+ has yet been found. increases the IEPS; dehydration and increased struc-
tural perfection decrease the IEPS. The IEPS’s
3. pH-Dependent Surface Modification of pure oxide materials can be quantitatively accounted
for in most cases by an electrostatic model involving
Raupach (99, 100) also found that the acid solubility the charge to radius ratio and the coordination number
of the oxyhydroxides and hydroxides of aluminum was with crystal field and hydration corrections.
characteristic of a-AI203 or amorphous Al(OH)3 (a- The IEPS and IEP are definitely related and are
AlOOH?) while the solubility in basic solutions was equal for many hydrous materials; however, for a
characteristic of a- or - 1( )3. This may reflect
significant number of materials there are other EP’s
recrystallization of the surface accompanying the which more closely approximate the IEPS. There
change in pH. (The relative stability of FeOOH and appear to be several mechanisms by which H+, OH-,
Fe203 is pH dependent. The reaction is slow in bulk and all hydroxo complexes present determine the
but presumably occurs quickly at the solid-solution surface charge on immersed oxide materials. Further
interface (117).) Normally the IEP is independent of work is needed to clarify the factors deciding which
the state of hydration or crystalline modification of the mechanism predominates in a given case, but it appears
solid phase because the free energy terms representing that for some materials adsorption of OH- and
the solid cancel in calculation of the equilibrium constant
Mz+(OH)z_i+ can be distinguished from amphoteric
for the net reaction dissociation of bound MOH groups.
M‘+(OH)»n-(aq) + 2H+ =
M‘+(OH)_i+(aq) + 2H20
Acknowledgments.—The author is grateful to the
U. S. Atomic Energy Commission for financial support
However, if the structure or composition of the solid
or its surface change with pH, the change must be
under Contract AT-(04-3) 326 PA #3. He wishes to
reflected either in the ionic concentrations used with express thanks to Drs. P. L. De Bruyn, R. B. Bhappu,
the equilibrium constant for this reaction or in calcula- H. C. Li, and G. Purcell, and Messrs. G. K. Korpi,
tion of the constant itself by taking into account the E. Volin, and O. L. Flaningham for permission to use
free energy involved in the solid change. For the unpublished data, and to Dr. G. E. Agar and Messrs.
J. H. Anderson, Jr., and G. K. Korpi for painstaking
Al(III) system, the IEP is pH 8.2 if calculated on the
reviews of the manuscript. Dr. de Bruyn deserves
assumptions that Al(OH)2+ is produced through
equilibration of the solution with an amorphous special thanks for stimulating initial interest in the
hydroxide surface and that Al(OH)4~ is produced subject. The patient typing and proofreading of many
drafts by Mrs. O. Baca and Mr. and Mrs. F. H.
through equilibration with an a-AI(OH)3 surface.
This value is in considerably better agreement with the Skelding are much appreciated.
observed IEPS for A1203 (hyd) (IEPS 9.2) than is the
=
nominal IEP (pH 7.5). The most basic IEP calculable VI. References
in this way for Fe203 assumes that the surface is (1) Abramson . A., Moyer, L. S., and Gorin, . H., “Elec-
amorphous hydroxide when acid and FeOOH when trophoresis of Proteins and the Chemistry of Cell Sur-
basic. The result, IEP =
9.0, is in excellent agreement faces,” Reinhold Publishing Corp., New York, N. Y.,
1942, p. 24 S.
with the most basic observed IEPS 9.0. In spite of
=
(5) Anderson P. J. “Proceedings, International Congress on (30) Flaningham, O. L., “The Electrokinetic Properties of
Surface Activity,” Butterworths Scientific Press, Lon- Goethite,” M. S. Thesis, Michigan College of Mining
don, 1957, p. 67. and Technology, 1960.
(6) Anderson, P. J., Trans. Faraday Soc., 54, 130 (1958). (31) Fricke, R., and Keefer, H., Nalurforsch., 4A, 76 (1949).
(7) Aplan, F. F., and Fuerstenau, D. W., “Froth Flotation, (32) Fricke, R., and Leonhardt, I., Naturwiss., 37, 428 (1950).
50th Anniversary Volume,” D. W. Fuerstenau, Ed., (33) Frink, C. R., and Peech, M., Inorg. Chem., 2, 473 (1963).
American Institute of Mining, Metallurgical and Petro- (34) Ganichenko, L. G., Kiselev, V. F., and Murina, V. V.,
leum Engineers, Inc., New York, N. Y., 1962, Chapter 7. Kinetika i Kataliz, 2, 877 (1961); Chem. Abstr., 58,
(8) Barany, R., U. S. Bur. Mines, Rept. Invest., 5825 (1961). 948c (1963).
(9) Basolo, F., and Pearson, R. G., “Mechanisms of Inorganic (35) Garrett, A. B., and Heiks, R. E., J. Am. Chem. Soc., 63,
Reactions,” John Wiley and Sons, Inc., New York, 562(1941).
N. Y., 1958: (a) p. 390; (b) p. 393; (c) p. 68; (d) pp. (36) Gaudin, A. M., and Fuerstenau, D. W., Trans. ,
44,54. 208,1365(1957).
(10) Bhappu, R. B., State Bureau of Mines and Mineral Re- (37) Gayer, K. H., and Garrett, A. B., Proc. Natl. Acad. Sci.
sources, N. M., Institute of Mining and Technology, India, A21, 11 (1952).
Socorro, personal communication, 1964. (38) Gayer, K. H., and Lieder, H., J. Am. Chem. Soc., 76, 5938
(11) Biedermann, G., and Schindler, P., Acta Chem. Scand., 11, (1954).
731(1957). (39) Gayer, K. H., and Lieder, H., J. Am. Chem. Soc., 77,1448
(12) Bikerman, J. J., “Surface Chemistry for Industrial Re- (1955).
search,” Academic Press, Inc., New York, N. Y., 1947, (40) Gayer, K. H., and Woontner, L., J. Phys. Chem., 60, 1569
p. 396. (1956).
(13) Bjerrum, J., Schwarzenbach, G., and Sillón, L. G., “Sta- (41) Gayer, K. H., and Woontner, L., J. Phys. Chem., 61, 364
bility Constants. Part II. Inorganic Ligands,” Special (1957).
Publication No. 7, The Chemical Society, London, 1958. (42) Gayer, K. H., Thompson, L. C., and Zajicek, D. T., Can.
(14) deBoer, J. H., Hermans, . E., and Vleeskins, J. M., Proc. J. Chem., 36, 1268 (1958).
Koninkl. Ned. Akad. Welenschap., 60, 45 (1957). (43) Gayer, K. H., and Thompson, L. C., Can. J. Chem., 36,
(15) deBoer, J. H., Linsen, B. G., and Okkerse, C., Koninkl. 1649(1958).
Ned. Akad. Welenschap, Proc., Ser. B, 63, 360 (1960). (44) Graham, K., and Madeley, J. D., J. Appl. Chem. (London),
(16) Bolzan, J. A., Janregui, E. A., and Arvia, A. J., Electro- 12, 485 (1962).
chim. Acta, 8, 841 (1963). (45) Grahame, D. C., Chem. Rev., 41, 441 (1947).
(17) Brosset C., Biedermann G., and Sillón, L. G., Acta Chem. (46) Green, J., Bull. Geol. Soc. Am., 70, 1127 (1959).
Scand., 8, 1917 (1954). (47) Hazel, F., and Ayres, G. H., J. Phys. Chem., 35, 2930
(18) Brown J., Jaap, W. J., and Ritchie, P. D., J. Appl. Chem. (1931).
(London), 9,153 (1959). (48) Herczyúska, E., and Prószyúska, K., Polish Academy of
(19) de Bruyn, P. L., and Agar, G. E., “Froth Flotation, 50th Sciences, Institute of Nuclear Research, Report No.
Anniversary Volume,” D. W. Fuerstenau, Ed., American 372/V, 1962 (Warsaw).
Institute of Mining, Metallurgical and Petroleum En- (49) Hückel, W. “Structural Chemistry of Inorganic Com-
gineers, Inc., New York, N. Y., 1962, Chapter 5. pounds,” Vol. I, Elsevier Publishing Co., New York,
(20) Chwastiak, S., in “Adaptation of New Research Tech- N. Y., 1950 p. 226.
niques to Mineral Engineering Problems,” Progress Re- (50) Issa, I. M., and Awad, S. A., J. Phys. Chem., 58, 948
port to USAEC NYO-10, 330( MITS-51)(Metallurgy- (1954).
General), No. 31, Oct. 1963. (51) Iwasaki, I., Cooke, S. R. B., and Choi, H. S., Trans.
(21) Clearfield, A., Inorg. Chem., 3, 146 (1964). , 217, 237(1960).
(22) Deltombe, E., de Zoubov, N., and Pourbaix, M., “Proceed- (52) Iwasaki, I., Cooke, S. R. B., and Colombo, A. F., U. S. Bur.
ings, Seventh International Committee of Electrochemi- Mines, Rept. Invest., 5593 (1960).
cal Thermodynamics and Kinetics (CITCE), London, (53) Iwasaki, I., Cooke, S. R. B., and Choi, H. S., Trans.
1955,” Butterworths Scientific Press, London, 1957, p. , 220, 394 (1961).
216 ff. (54) Iwasaki, I., Cooke, S. R. B., and Kim, Y. S., Trans. ,
(23) Deltombe, E., de Zoubov, N., and Pourbaix, M., “Pro- 223,113(1962).
ceedings, Ninth International Committee of Electro- (55) Johansen, P. G., and Buchanan, A. S., Australian J.
chemical Thermodynamics and Kinetics (CITCE), Chem., 10,392(1957).
Paris, 1957,” Butterworths Scientific Press, London, (56) Johansen, P. G., and Buchanan, A. S., Australian J. Chem.,
1959, p. 117 S. 10,398(1957).
(24) Dobiái, B., Spurn#, J., and Freudlová, E., Collection (57) Johnston, H. L., Cuta, F., and Garrett, A. B., J. Am. Chem.
Czech. Chem. Commun., 24, 3668 (1959). Soc., 55,2311(1933).
(25) Downey, B. J., paper presented at the 1959 Meeting of the (58) Joy, A. S., Watson, D., and Cropton, R. G. W., Trans.
Physical Chemistry Division of the American Chemical , 229,5(1964).
Society. (59) Korpi, G. K., “Measurement of Streaming Potentials,”
(26) Dugger, D. L., Stanton, J. H., Irby, B. N., McConnell, M. S. Thesis, Department of Metallurgy, MIT, 1960.
B. L., Cummings, W. W., and Maatman, R. W., J. (60) Kovalenko, P. N., Fiz.-Khim. Metody Issled. Vozdushn.
Phys. Chem., 68, 757 (1964). Sredy, 80(1961).
(27) El Wakkad, S. E. S., and Rizk, H. A., J. Phys. Chem., 61, (61) Kovalenko, P. N., and Bogdasarov, K. N., Russ. J.
494(1957). Inorg. Chem., 6, 272 (1961).
(28) Emerson, K., and Graven, W. M., J. Inorg. Nucí. Chem., (62) Kossiakoff, A., and Barker, D., J. Am. Chem. Soc., 60,
11, 309 (1959). 2047 (1938).
(29) Feitknecht, W., and Schindler, P., Pure Appl. Chem., 6, (63) Koz’mina, Z. P., Belova, . P., and Sannikov, V. A.,
130(1963). Kolloidn. Zh., 25, 169 (1963).
Isoelectric Points of Solid Oxides and Hydroxides 197
(64) Krause, A., and Borkowska, A., Roczniki Chem., 29, 999 (94) Pourbaix, M., “Enthalpies Libres de Formation Standards,
(1955); Chem. Abstr., 50, 7550? (1956). A 25°C,” Rapport Technique No. 28, Centre Beige
(65) Latimer, W. M., “The Oxidation States of the Elements de’Etude de la Corrosion, Brussels, 1955.
and Their Potentials in Aqueous Solutions,” 2nd Ed., (95) Pourbaix, M., de Zoubov, N., and Deltombe, E., “Pro-
Prentice-Hall, Inc., New York, N. Y., 1952. ceedings, Seventh International Committee of Electro-
(66) Lengweiler, H., Buser, W., and Feitknecht, W., Helv. chemical Thermodynamics and Kinetics (CITCE),
Chim. Acta, 44, 796 (1961). London, 1955,” Butterworths Scientific Press, London,
(67) Lengweiler, H., Buser, W., and Feitknecht, W., Helv. 1957.
Chim. Acta, 44,805 (1961). (96) Pravdic, V., and Sotman, S., Croat. Chem. Acta, 35, 247
(68) Li, H. C., “Adsorption of Inorganic Ions on Quartz,” (1963).
Sc.D. Thesis, Department of Metallurgy, MIT, 1958. (97) Purcell, G., and Sun, S. C., Trans. , 226, 6 (1963).
(69) Liberti, A., Chiantella, V., and Corigliano, F., J. Inorg. (98) Rao, G. S., “Adsorption of Amine on Manganese Dioxide,”
Nucí. Chem., 25, 415 (1963). M.S. Thesis, Department of Metallurgy, MIT, 1959.
(70) Marcus, Y., Acta Chem. Scand., 11, 690 (1957). (99) Raupach, M., Australian J. Soil Res., 1, 28 (1963).
(71) Mattson, S., Soil Sci., 30, 459 (1930). (100) Raupach, M., Australian J. Soil Res., 1, 55 (1963).
(72) Mattson, S., and Pugh, A. J., Soil Sci. 38, 229 (1934). (101) Ray, K., in “Adaptation of New Research Techniques to
Mineral Engineering Problems,” Progress Report to
(73) McDonald, R. S., J. Phys. Chem., 62, 1168 (1958).
(74) Miaw, H. L., “The Effect of Iron Oxide Slime Coatings on
USAEC, NYO-10, 330(MITS-51) (Metallurgy-General),
Flotation of Quartz and Other Minerals,” M.S. Thesis, No. 31, Oct. 1963, with permission of P. L. de Bruyn,
Department of Metallurgy, MIT, 1957. Department of Metallurgy, MIT.
(102) Razouk, R. I., and Mikhail, R. S., J Phys. Chem., 62, 920
(75) Michaelis, L., “Hydrogen Ion Concentration. Vol. I.
(1958).
Principles of the Theory,” Williams and Wilkins Co.,
(103) Robinson, M., Pask, J. A., and Fuerstenau, D. W., J. Am.
Baltimore, Md., 1926, pp. 258-263. Ceram. Soc., 47, 516 (1964).
(76) Modi, H. J., and Fuerstenau, D. W., J. Phys. Chem., 61, (104) Rollinson, C. L., “The Chemistry of the Coordination Com-
640(1957).
pounds,” J. C. Bailar, Ed., Reinhold Publishing Corp.,
(77) Moeller, T., “Inorganic Chemistry, An Advanced Text- New York, N. Y., 1956, Chapter 13.
book,” John Wiley and Sons, Inc., New York, N. Y., (105) Rossini, F. D., Wagman, D. D., Evans, W. H., Levine, S.,
1952, Chapter 9, especially pp. 318-321. and Jaffe, I., “Selected Values of Chemical Thermo-
(78) Moulik, S. P., and Ghosh, B. N., J. Indian Chem. Soc., 40, dynamic Properties,” U. S. Bureau of Standards, Cir-
907 (1963). cular 500, 1952.
(79) O’Connor, D. J., and Buchanan, A. S., Australian J. Chem., (106) Rossotti, F. J. C., and Rossotti, H., Acía Chem. Scand.
6,278(1953). 10,957(1956).
(80) O’Connor, D. J., Johansen, P. G., and Buchanan, A. S., (107) Russell, A. S., Edwards, J. D., and Taylor, C. S., Trans.
Trans. Faraday Soc., 52, 229 (1956). , 203, 1123 (1955).
(81) O’Connor, D. J., and Buchanan, A. S., Trans. Faraday (108) Schindler, P., Althaus, H., Schürch, A., and Feitknecht,
Soc., 52,397(1956). W., Chimia (Aarau), 16, 42 (1962).
(82) Okkerse, C., deBoer, J. H., and Cyrot, Mme., J. chim. (109) Schindler, P., Michaelis, W., and Feitknecht, W., Helv.
phys., 57, 534 (1960). Chim. Acta, 15, 444 (1963).
(83) Overbeek, J. Th. G., “Colloid Science. Vol. I. Irreversible (110) Schuylenborgh, J., Trans. Intern. Congr. Soil Sci., 4th,
Systems,” H. R. Kruyt, Ed., Elsevier Publishing Co., Amsterdam, 1950, Vol. I, p. 89; Vol. II, p. 63.
New York, N. Y., 1952, Chapter IV: (a) p. 160; (b) p. (111) Schuylenborgh, J., Rec. trav. chim., 70, 985 (1951).
169; (c) p. 134. (112) Schuylenborgh, J., and Sanger, A. . H., Rec. trav. chim.,
(84) Palache, C., Berman, H., and Frondel, C., “The System 68,999(1949).
of Mineralogy,” Vol. I, 7th Ed., John Wiley and Sons, (113) Schuylenborgh, J., Arens, P. L., and Kok, J. G. J., Rec.
trav. chim., 69, 1557 (1950).
Inc., New York, N. Y., 1951.
(114) Sen, K. C., and Ghosh, B. N., J. Indian Chem. Soc., 33, 209
(85) Parks, G. A., “A Study of the Surface of Ferric Oxide in
(1956).
Aqueous Systems,” Ph.D Thesis, Department of Met-
(115) Seshaiah, U. V., and Banerji, S. N., J. Indian Chem. Soc.,
allurgy, MIT, 1960.
39,93(1962).
(86) Parks, G. A., unpublished data. (116) Shankar, J., and de Souza, B. L., Australian J. Chem., 16,
(87) Parks, G. A., and de Bruyn, P. L., J. Phys. Chem., 66, 1119(1963).
967(1962). (117) Smith, F., and Kidd, D. J., Am. Mineralogist, 34, 403
(88) Parreira, H. C., and Ottewill, R. H., Anais Acad. Brasil. (1949).
Cienc., 32,35 (1960). (118) Sowden, R. G., and Francis, K. E., Nucí. Sci. Eng., 16, 1
(89) Pauling, L., “The Nature of the Chemical Bond,” 3rd Ed., (1963).
Cornell University Press, Ithaca, N. Y., 1960, pp. 276, (119) Tewari, S. N., and Ghosh, S., Proc. Natl. Acad. Sci. India,
557. A21, 29(1952).
(90) Perrin, D. D., J. Chem. Soc., 3189 (1960). (120) Tewari, N., and Ghosh, S., Kolloid-Z., 138, 93 (1954).
(91) Perrin, D. D., J. Chem. Soc., 4500 (1962). (121) Troelstra, S. A., and Kruyt, H. R., Kolloid-Z., 101, 182
(92) Pinto, L., Egger, K., and Schindler, P., Helv. Chim. Acta, (1942).
46,425(1963). (122) Van Lier, J. A., de Bruyn, P. L., and Overbeek, J. Th. G.,
(93) Pitman, A. L., Pourbaix, M., and de Zoubov, N., in “Pro- J. Phys. Chem., 64, 1675 (1960).
ceedings, Ninth International Committee on Electro- (123) Verwey, E. J. W., Rec. trav. chim., 60, 625 (1941).
chemical Thermodynamics and Kinetics (CITCE), (124) Weiser, . B., “Inorganic Colloid Chemistry, II, the Hy-
Paris, 1957,” Butterworths Scientific Press, London, drous Oxides and Hydroxides,” John Wiley and Sons,
1959. Inc., New York, N. Y„ 1935, p. 142.
198 George A. Parks
(125) Wells, A. F., “Structural Inorganic Chemistry,” Clarendon stants of Complex Compounds,” Pergamon Press, New
Press, Oxford, 1962: (a) p. 457; (b) p. 878. York, N. Y., 1960.
(126) Welo, L. A., and Baudisch 0., Chem. Rev., 15, 45 (1934). (129) Yopps, J. A., and Fuerstenau, D. W., J. Colloid. Sei., 19,
61(1964).
(127) WyckoS, R. W. G., “Crystal Structures,” Vol. I, Inter-
(130) Young, G. J., J. Colloid Sci., 13, 67 (1958).
science Publishers, New York, N. Y., 1960. (131) Zhabrova, G. M., and Egorov, E. V., Russ. Chem. Rev.,
(128) Yatsimirskii, K. B., and Vasil’ev, V. P., “Instability Con- 30,338(1961).