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Experimental data on the solubility of mercury oxide (HgO) in various aqueous solutions, including hydrofluoric acid (HF), sodium hydroxide (NaOH), potassium hydroxide (KOH), and sodium hydroxide with different concentrations. The document also includes information on the preparation of the solutions, the experimental procedure, and the sources and purity of materials.
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(1) Mercury(II) oxide; HgO; [21908-53-2]
(2) Hydrofluoric acid; HF; [7664-39-3]
(3) Water; H 2
Concentration of HF at 25°C.
T. P. Dirkse
Solubility of HgO in aqueous HF at 25°C.
-3 (^) g Hg/9.6 - cHF/mol dm ccm^ CHgO/mol^ dm
The solid phase is not identified but the implication is that it is HgO.
The concentration of HgO varies almost linearly with the concentration of HF. The author concludes from this that the reaction of dissolution is
i.e., the molecular formula of hydrogen fluoride is H 2 F 2 •
In additional experiments, details of which are not included in the article, the solubility of HgO in aqueous HF was found to decrease when KF was added to the aqueous HF. The author attributes this to the lack of formation of mercury fluoride complexes.
Mixtures of red HgO and aqueous HF were shaken in a thermostat at 25°C. The mercury content of the saturated solutions was de- termined by electrolysis. No information is given about the length of time the mixtures were shaken. The glass apparatus was protected from attack by the HF by coating it with bee's wax or a commercially available gelatin-like material.
The materials were of a chemically pure grade.
No details are given.
320 Mercury(ll) Oxide
(1) Mercury(II) oxide; RgO; [21908-53-2]
(2) Barium hydroxide; Ba(OR)2; [17194-00-2]
(3) Water; R 2 0; [7732-18-5]
Red and yellow RgO were used at 25°C.
T. P. Dirkse
yellow RgO
red RgO
Table I Solubility of RgO in water at 25.0 0 C.
0.0518 g dm- 3 2.39 x 10- 4 mol dm- 3 a
0.0513 g dm- 3 2.37 x 10-
mol dm- 3 a
a Calculated by compiler.
Table II
Solubility of yellow RgO in barium hydroxide solutions at 25.0°C.
mol Ba(OR)2 dm-3 g RgO dm-3 mol RgO dm-3 a
a'Calculated by compiler.
2.71 x 10- 4
6.29 x 10- 4
Oxide-solvent mixtures were shaken in a closed vessel in a thermostat for a week, allowed to settle for 36 hours, and filtered The mercury content was determined by two methods: (a) add 5 g NaCl to 100 ml of solution, heat to boiling and cool to 40-50° , add phenolphthalein and titrate the NaOR pro duced by this reaction with RCl; (b) evapora e an aliquot of the solution to dryness and weigh the residue. Equilibrium was approach ed from both supersaturation and under saturation.
Conductivity water and purified forms of the red and yellow RgO were used.
The impurities in the oxides were estimated at less than 0.005%.
322 Mercury(1I)^ Oxide
COMPONENTS: (1) Mercury(II) oxide; HgO; [21908-53-2]
(2) Lithium hydroxide; LiOH; [1310-65-2]
(3) Water; H 2
Lithium hydroxide concentration at 25°C.
Garrett, A. B.; Hirschler, A. E.
T. P. Dirkse
Solubility of yellow HgO in LiOH solutions at 25°C.
mol LiOH/kg H 2
(mol HgO/kg H 2
Samples of HgO and solvent were sealed in nitrogen-filled flasks and shaken for 3 weeks at 25°C. Other mixtures were shaken at 42°C for about 3 days and then at 25°C for 3 weeks. After agitation, the samples were allowed to sediment for 4 da)s, then filtered through a sintered glass filter. Alkali concentration was determined by weight titration using methyl o~ange indi- cator. Mercury content was determined by potentiometric titration with KI (1).
Two different preparations of yellow lIg were used. Reagent grade LiOH was dis- solved in water and allowed to stand for a while so that the slight precipitate could settle out. Conductivity water was used throughout.
Mercury analysis had a reproducibility with- in 0.5% The alkali analysis had an error of less than 5%. Separate solubility values were within 2% of the avera~e.
REFERENCES:
Mercury(ll) Oxide 323
(1) Mercury(II) oxide; HgO; [21908-53-2]
(2) Potassium hydroxide; KOH; [1310-58-3]
(3) Water; H 2 0; [7732-18-5]
Concentration of KOH at 25°C.
Garrett, A. B.; Hirsch1er, A. E.
T. P. Dirkse
Solubility of yellow HgO in KOH solutions at 25°C.
mol KOH/kg H 2
5 (mol HgO/kg H 2 0)x 10
Samples of HgO and solvent were sealed in nitrogen-filled flasks and shaken for 3 weeks at 25°C. Other mixtures were shaken at 42°C for about 3 days and then at 25°C for 3 weeks After agitation, the samples were allowed to sediment for 4 days, then filtered through a sintered glass filter. Alkali concentration was determined by weight titration using methyl orange indicator. Mercury content was determined by potentiometric titration with KI (1).
Two different preparations of yellow HgO were used. The hydroxide solutions were carbonate-free. Conductivity water was used throughout.
Mercury analysis had a reproducibility with- in 0.5%. The alkali analysis had an error of less than 5%. Separate solubility values "',." ",i ~hi" ?OJ nJ' ~h" REFERENCES:
(1) Mercury(II) oxide; HgO; [21908-53-2]
(2) Sodium hydroxide; NaOH; [1310-73-2]
) (3) Water; H 2 0; [7732-18-5]
Sodium hydroxide concentration at 25°C.
Garrett, A. B.; Hirschler, A. E.
T. P. Dirkse
Solubility of red HgO in NaOH solutions at 25°C.
mol NaOH/kg H 2
O (mol HgO/kg H 2 O)^
x 105
0.1064 22.7 (^) (s) 0.3398 (^) 23. 0.4406 (^) 24.2 (s) 0.5818 (^) 24. 0.7223 (^) 25.1 (u) 1.001 (^) 26. 1.638 (^) 27. 1.987 27.6 (u) 2.940 29. 3.956 29. 4.936 29.
(s) equilibrium approached from supersaturation only.
(u) equilibrium approached from undersaturation only.
Samples of HgO and solvent were sealed in nitrogen-filled flasks and shaken for 3 weeks at 25°C. bther mixtures were shaken at 42°C for about 3 days and then at 25°C for 3 weeks After agitation, the samples were allowed to sediment for 4 days, then filtered through a sintered glass filter. Alkali concentratio was determined by weight titration using meth 1 orange indicator. Mercury content was deter- mined by potentiometric titration with KI (1)
Five different preparations of red HgO were used. The hydroxide solutions were carbonate-free. Conductivity water was used throughout.
Mercury analysis had a reproducibility with in 0.5%. The alkali analysis had an error of less than 5%. Separate solubility value were within 2% of the average. REFERENCES:
(1) Mercury(II) oxide; HgO; [21908-53-2] (2) Nitric acid; HN0 3 ; [7697-37-2] (3) Water; H 2 0; [7732-18-5)
Concentration of HN 3
at 25°C.
T. P. Dirkse
Table I
Solubility of red HgO in aqueous nitric acid solutions.
(moles HNO/ 3 (moles HNO/ 3 (moles^ HgO/^4 kg H 2 0) x 0 kg H 2 0)^ x^0 kg H 2 0)^ x 10 as samples were from^ pHa made up
0.100 0.14^ 2. 0.200 0.07^ 3. 0.300 0.14 2.77^ (u) 0.500 0.30^ 3.48^ (s) 0.700 0.38 3. 0.900 0.48 4.02 (u) 2.00 2.5^ 6. 3.00 1.9 9. 5.00 3.8^ 14. 7.00 4.1^ 20. 9.00 5.0^ 27. 20.0 7.3^ 64.2^ (s)
a The value of H+ so determined was divided by the activity coefficient of HN 3
(s) equilibrium approached from supersaturation only.
(u) equilibrium approached from undersaturation only.
Samples of HgO and solvent were sealed in nitrogen-filled flasks and shaken for 3 weeks at 25°C. Other such preparations were agi- tated for about 3 days at 42°C, then trans- ferred to a 25°C. thermostat for 3 weeks. After the agitation the samples were allowed to sediment for about 4 days before analysis. The nitric acid solutions were prepared by dilution of standard solutions. pH was measured after equilibrium by using a glass electrode. Mercury content was determined by potentiometric titration with KI (2).
Materials were reagent grade. Conductivity water was used to make all solutions.
Nothing is stated and only averages of pairs of values are given.
(1) Mercury(II) oxide; HgO; [21908-53-2]
(2) Hydrochloric acid; HCl; [7647-01-0]
(3) Water; H 2 0; [7732-18-5]
Garrett, A.B.; Lemley, J.
Concentration of hydrochloric acid. The temperature is not stated but from compari- sonwith other work it apparently is 25°C.
T. P. Dirkse
EXPERIMENTAL VALUES: (^) Table I
Solubility of yellow HgO in aqueous HCl solutions
(s) equilibrium approached (u) equilibrium approached
(moles HgO/ 4 kg H 2 0) x 10
36
18.6(u)
56
31
19.8(u) 22.8(u) 34 (s) 47 (s) 232 (u) 414 (s) 534 (s) 1490 (s) 1480 (s)
(moles HCl/ kg H^2 2
from supersaturation only. from undersaturation only.
(moles HgO/ (^4) kg H 2 0) x 10
2.47(s)
7
25.8(u)
20.l(u)
(moles HCl/ 2
Solid HgO was added to solutions and Reagent grade chemicals and conductivity shaken. Solubility was approached from water were used. under saturation and from supersaturation. The general procedure is the same as that used earlier (1).
No estimate is given and the precision of the analyses cannot be inferred from the data given.
Mercury(lll Oxide 329
(1) Mercury^ (II)^ oxide;^ HgO;^ [21908-53-2]^ Garrett,^ A.B.;^ Lemley,^ J. J. Am. Chern. Soa., 1942,64, 2380-3. (2) Hydrochloric^ acid;^ HCl;^ [7647-01-0]
(3) Water; H 2
EXPERIMENTAL VALUES continued •..
Table II
Solubility of yellow HgO in aqueous HCl solutions
moles HCl/kg H 2
O (moles HgO/ (^4) pH a^ Solid phase kg H 2
0.00100 9.0 5.0 yellow 0.00300 20.8 4.9 yellow 0.00500 3.18 4.9 yellow 0.00700 40.7 4.7 yellow lie black 0.0090 28.9 4.9 yellow lie black 0.0120 30.9 5.1 yellow lie black 0.0160 29.1 5.0 yellow lie black 0.0200 22.1 4.8 yellow lie black 0.0300 15.0 5.0 yellow lie black 0.0400 10.0 5.2 yellow lie black 0.0500 21.6 5.1 brown 0.1007 82 4.0 black 0.1210 237 4.1 black 0.1412 387 4.2 black 85. 0.1614 (^545) 4.0 black 0.201B 8BO 3.8 black 85. 0.2425 1150 3.9 black 85. 0.2832 1410 black 85.
adetermined with a glass electrode
SD8 /.23-L
(1) Mercury (II) oxide; HgO; [21908-53-2] (2) Sodium perchlorate; NaCl 4
(3) Water; H 2 0; [7732-18-5]
T. P. Dirkse
Table I
Solubility of red HgO in 3 mol dm^ -3 NaCl 4
solutions.
Concentrations are expressed as mol dm
-log [HgO]
The solvents were allowed to percolate through a column containing the solid red HgO. The solid waflirradiated f2r 3 h~urs in a flux of 5.5 x 10 neutrons cm sec • Mercury content was determined by taking a weighed sample, counting the gamma radiation and comparing it with a carefully prepared and analyzed standard. pH measurements were made with a glass electr023' pH was adjusted by adding 0.01 mol dm NaOH or HCl0 4 •
Reagent grade materials and conductivity water were used.
ESTIMATED ERROR: Analyses for individua!5sam- pIes had a standard deviation of 6 x 10 , but successive samples from a given system varied by 5% of the measured value. No in- dication is given as to how precisely the
332 Mercury(lll^ Oxide
(1) Mercury(II) oxide; HgO; [21908-53-2]
(2) Sodium sulfide; Na 2 S; [1313-82-2]
(3) Water; H 2 0; [7732-18-5]
Concentration of sodium sulfide at 25°C
Milyutina, N. A.; Polyvyannyi, I. R.;
T. Michalowski
Solubility of HgO in aqueous Na 2 S at 25°C
mol S2- dm-3 mol Hg(II) dm-3 Ionic Strength, mol dm- 3
Activity coefficient of Hg(II)
No details are given, but from other work reported by these authors it appears that equilibrium was reached isothermally after agitation for about a day.
The HgO and Na 2 S were analytical grade materials.
This cannot be estimated from the limited amount of information given in the paper.
(1) Mercury(II) oXide; RgO; [21908-53-2]
(2) Potassium hydroxide; KOR; [1310-58-3]
(3) Water; R 2
Concentration of KOR and temperature.
T. P. Dirkse
Solubility (^) of RgO in aqueous KOR a.
10 CRgO/mol dm
t/oC (^) Ab^ B C (^) D E -- -- --^ -- -- -- 25 2.8 3.1 3.2 2.7 2. 35 4.1 4.4 4.4 3.7 2. 45 5.8 6.1 5.8 4.8 3. 55 8.1 8.1 7.3 5.9 5.
a These values are not included in the original article, but were supplied by the authors in a personal communication.
B = 5; C = 10; D = 20; E = 30.
The e.m.f. of the following cell was measured:
HgIHg(II),KOH(aq) IKOH(aq) IHgO(s) IHg
The KOH concentration was the same in both cell compartments. The concentration of Hg(II) in the left cell compartment was prepared accurately and was less than 50% of the concentration in the right cell compartment. The temperature was controlled to within O.loC.
The Hg, HgO and KOH were reagent grade materials. The water was distilled twice.
Less than 5%.