Names | |
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IUPAC name
Pentazinc dichloride octahydroxide monohydrate
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Other names
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Identifiers | |
3D model (JSmol)
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Properties | |
Zn5(OH)8Cl2·H2O | |
Molar mass | 551.87 g·mol−1 |
Appearance | White or colorless crystalline solid |
Density | 3.3 g/cm3 |
Insoluble in water, pH 6.9 measured by EPA method SW846-9045 | |
Solubility | Insoluble in organic solvents |
Structure | |
Hexagonal | |
Octahedral and tetrahedral | |
Hazards | |
NFPA 704 (fire diamond) | |
Flash point | Non-flammable |
Safety data sheet (SDS) | [1] |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Zinc chloride hydroxide monohydrate or more accurately pentazinc dichloride octahydroxide monohydrate is a zinc hydroxy compound with chemical formula Zn5(OH)8Cl2·H2O. It is often referred to as tetrabasic zinc chloride (TBZC), basic zinc chloride, zinc hydroxychloride, or zinc oxychloride. It is a colorless crystalline solid insoluble in water. Its naturally occurring form, simonkolleite, has been shown to be a desirable nutritional supplement for animals.
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Transcription
Greetings fellow nerds. In an upcoming video we're going to make glow in the dark phosphorescent powder from the chemicals we've been making in previous videos. However, the aluminum and strontium nitrates must be extremely pure. Impurities will interfere with the phosphorescent process. So in this video, we'll use the technique of recrystallization to purify them from 90% purity up to 99.9%. Recrystallization works because crystals tend to be purer than the solutions they came from. As long as you discard the solution before the impurities also crystallize out, you'll have purer crystals of your product. Repeating the process further increases purity. The downside is that you lose alot of your product as well. In addition, this works best if your product is also reasonably pure. If you have more contaminants than product the contaminants will crystallize before your product does. So first let's start with aluminum nitrate. As you can see here it’s not perfectly white as it should be, so we'll first need a pre-filtering step. Just enough water to completely dissolve it. As you can see the aluminum nitrate actually has lots of brown particles in it. Simply filter them out to get a clear liquid. Now we couldn't filter these out in the previous video because when the solution is first made, the particles are too fine to be filtered let alone be seen by eye. The solution must first be crystallized once to cause the particles to aggregate into something big enough that can be filtered. Here it is after filtering, nice and clear. Now dry it out and use the desiccator bag if needed. Now you have clear aluminum nitrate nonahydrate. Now, we can go on to the actual recrystallization. Here I’ve mixed a lot of batches of aluminum nitrate nonahydrate and already filtered and dried it. Accurately weigh how much you have before starting. Here i have fifty grams of aluminum nitrate nonahydrate. now accurately add in 20% of it's mass in distilled water. So since I have fifty grams, I’m adding in 10 mL of distilled water. It won't all dissolve so heat it up until it does. It'll turn slightly yellow but this is not a problem. Ok once the solution is completely clear, cover it up and let it slowly cool down to room temperature. After a few hours of cooling you can see it has formed these very large crystals of aluminum nitrate. The impurities are now concentrated in the liquid layer. So now, pour off the liquid and break up the crystals. There they are. Now weigh them again. Ok so the total weight now is about 33g. We're going to recrystalize it one more time for even better purity. So once again add in 20% distill water, in this case it's 6.6mL and again heat until it dissolves. And then allow to cool. Pour off the impurities in the liquid. Now you can dry the crystals. I recommend using the desiccator bag. Now we have 18 grams of ultra pure aluminum nitrate nonahydrate. Although we lost 32 grams during the two recrystallization steps our objective was best quality not greatest quantity, Now we're going to purify strontium nitrate. Get a wide beaker and place in a quantity of strontium nitrate that we already made in a previous video. Add in just enough water to dissolve the strontium nitrate. It's very slighly cloudy so filter it off to get a clear solution. Then this time, leave in air to dry. We can't use the heating and cooling method like aluminum nitrate because the solubility of strontium nitrate doesn't change that much with temperature as with aluminum nitrate. So we'll have to evaporate the slow way. Evaporate it down until you have about 10 to 20% liquid left. I started with ten militers so i evaporated down to about 2mL of liquid not including the crystals. Get rid of the liquid. And once again repeat the process of dissolving and crystallizing. Once again I recommend using the desiccator bag to dry the final product. Now we have ultra-pure strontium nitrate. We are now ready to make glow in the dark phosphorescent powder in our next video. So please subscribe, rate, and comment. Note: Distilled water should be used for the dissolving steps. Using tap water won't improve the purity as much as distilled water. Deionized water can be used but it won't be as good as distilled water.
Natural occurrence
The naturally occurring mineral form, simonkolleite, was described as a new mineral in 1985 for samples collected at Richelsdorf, Germany. It is a rare secondary mineral formed by weathering of zinc-bearing slag, and is associated with native zinc, hydrocerussite, diaboleite, zincite and hydrozincite. It is named after Werner Simon and Kurt Kolle, Mineral collectors of Cornberg, near Michelsdorf who submitted the samples for investigation. Simonkolleite is frequently found as a corrosion product of Zinc bearing metals.[1][2][3][4]
Structure
Simonkolleite is rhombohedral, space group R3m. There are two crystallographically distinct zinc sites in Simonkolleite, both of which are fully occupied by zinc. The Zn(1) site is coordinated by six hydroxyl (OH) groups in an octahedral geometry [Zn(OH)6]. The Zn(2) site is coordinated by three OH groups, and one Cl atom in a tetrahedral geometry [Zn(OH)3Cl]. The [Zn(OH)6] octahedra form an edge-sharing dioctahedral sheet similar to that observed in dioctahedral micas. On each site of the vacant octahedron, a [Zn(OH)3Cl] tetrahedron is attached to three anions of the sheet and points away from the sheet. Intercalated between adjacent sheets are interstitial water (H2O) groups. The sheets are held together by hydrogen bonding from OH groups of one sheet to Cl anions of adjacent sheets, and to interstitial H2O groups. The [Zn(OH)6] octahedra have four long equatorial bonds (at 2.157 Å) and two short apical bonds (at 2.066 Å). This apical shortening is a result of the bond-valence requirements of the coordinating OH groups and the connectivity of polyhedra in the structure. The equatorial OH groups [O(1)H] are coordinated by two Zn(1) cations and one Zn(2) cation, whereas the apical OH groups [O(2)H] are coordinated by three Zn(1) cations. As Zn(1) is six-coordinated and Zn(2) is four-coordinated, the local bond-valence requirements require the Zn(1)-O(1) bonds to be considerably longer than the Zn(1)-O(2) bonds. The [Zn(OH)3Cl] tetrahedron has three short Zn(2)-O(1) bonds (at 1.950 Å) and one long Zn(2)-Cl bond (2.312 Å) (Figure 1).[1][2][3]
Properties
Simonkolleite is colorless, forms tabular hexagonal crystal up to 1 mm in diameter, and has perfect cleavage parallel to (001).[3]
Thermal stability studies have shown that simonkolleite decomposes to ZnO at several stages upon heating (eq. 1-3).[5][6][7][8] The decomposition starts with loss of a single mole of the lattice water. Further dehydration at 165−210 °C produces a mixture of ZnO and an intermediate Zn(OH)Cl. At 210−300 °C, the intermediate Zn(OH)Cl decomposes to ZnO and ZnCl2. At higher temperature, volatilization of zinc chloride occurs, leaving a final residue of zinc oxide.
-
Zn5(OH)8Cl2·H2O Zn5(OH)8Cl2 + H2O
(eq. 1)
-
Zn5(OH)8Cl2 2 Zn(OH)Cl + ZnO + H2O
(eq. 2)
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2 Zn(OH)Cl ZnCl2 + ZnO + H2O
(eq. 3)
The dehydrated mixture (Zn(OH)Cl and ZnO) is easily rehydrated and converted back to simonkolleite upon exposure to cool moist air (eq. 4).[5][6][7]
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2 Zn(OH)Cl + 3 ZnO + 4 H2O Zn5(OH)8Cl2·H2O
(eq. 4)
Simonkolleite is virtually insoluble in water and organic solvents, soluble in mineral acids yielding the corresponding zinc salts (eq. 5), soluble in ammonia, amine and EDTA solutions under complex formation. It can easily be converted to zinc hydroxide by reacting with sodium hydroxide (eq. 6). Its pH in water is 6.9 measured by EPA method SW846-9045.[9]
-
Zn5(OH)8Cl2·H2O + 8 HCl → 5 ZnCl2 + 9 H2O
(eq. 5)
-
Zn5(OH)8Cl2·H2O + 2 NaOH → 5 Zn(OH)2 + 2 NaCl + H2O
(eq. 6)
Preparation
From hydrolysis of ZnCl2
Basic zinc chloride can be prepared by hydrolysis of a ZnCl2 solution in the presence of a base such as sodium hydroxide or ammonia (eq. 7-8).[5][10]
-
5 ZnCl2 + 8 NaOH + H2O → Zn5(OH)8Cl2·H2O + 8 NaCl
(eq. 7)
-
5 ZnCl2 + 8 NH3 + 9 H2O → Zn5(OH)8Cl2·H2O + 8 [NH4]Cl
(eq. 8)
Simonkolleite nanodisks with a width of 40 nm have been successfully synthesized via a hydrothermal method using zinc chloride and ammonia as the starting materials.[10]
From reaction of ZnCl2 with ZnO
Basic zinc chloride can be synthesized from the reaction of a ZnCl2 solution with ZnO (eq. 9).[11][12][13]
-
ZnCl2 + 4 ZnO + 5 H2O → Zn5(OH)8Cl2·H2O
(eq. 9)
It can be synthesized from nano-sized ZnO particles aged in aqueous ZnCl2 solution at 6–140 °C for 48 h. Elevating the aging temperature increases the crystallinity of basic zinc chloride.[13]
Applications
As a feed additive and nutrition supplement for animals
Zinc is an essential trace element for all animals. It is found in all organs and tissues of the body, with bone, muscle, liver, kidney, and skin accounting for the majority of body zinc. Zinc is commonly added to diets for animals in a supplemental form, usually as inorganic feed-grade zinc oxide or zinc sulfate hydrate, or one of the organic zinc chelates and complexes. In several experiments, zinc oxide has been shown to be less bioavailable for poultry and pigs than reagent-grade or feed-grade zinc sulfate; however, the sulfate forms are highly water-soluble and thus also hygroscopic under humid conditions.[14][15]
Tetrabasic zinc chloride (Simonkolleite), a zinc hydroxy mineral, is a new form of zinc nutrition supplement for animals. When TBZC is made by a crystallization process (Micronutrients TBZC), it excludes contaminating ions, providing a product with greater purity and fewer dust particles than occurs with precipitation. The result is a crystalline solid that is essentially insoluble in water, non-hygroscopic, un-reactive in most foods or feedstuffs, and yet highly bioavailable.[14][15][16][17]
Since TBZC is neutral and water-insoluble, it has excellent palatability and very low interactions with other ingredients in a food mixture compared to zinc chloride, zinc sulfate or chelated forms of the metal. It also avoids the problems with caking.[14]
It has been shown that the relative zinc bioavailability for chicks in TBZC is two to three times higher than that in Waselz-processed ZnO.[14][15]
Research studies performed at universities and feed industry have all indicated that TBZC has a higher bioavailability relative to zinc sulfate, with values ranging from 102 to 111%.[15][16] Four studies comparing TBZC to zinc oxide as a growth promoter all indicate improved weight gain and feed conversion at lower levels using TBZC.[17][18][19][20][21] Testing in vitro has shown better antimicrobial activity with TBZC than both zinc sulfate and zinc oxide.[17][21][22] Investigation on growth performance and some physiological parameters in the digestive tract of weanling piglets has shown that TBZC stimulated the synthesis and secretion of pancreatic chymotrypsin and may promote intestinal health.[22]
As a stabilizing agent in nutritional and fungicidal compositions
Basic zinc chloride has been used as a stabilizing agent in nutritional and fungicidal compositions for application to the foliage of growing plants.[23]
As a Zn supplementation to metalloprotease therapy
Tetrabasic zinc chloride has been used as a Zn supplementation for increasing responsiveness to therapeutic metalloproteases, including increasing and/or maximizing responsiveness and preventing botulinum and tetanus toxin resistance due to a functional deficiency of zinc.[24]
In oral compositions
Basic zinc chloride has been used as a therapeutically active agent in oral compositions for the care of teeth.[25]
In coating compositions
Basic zinc chloride, in combination with water-soluble alkali metal silicate, is used to coat substrates normally infested by algae, such as concrete roofing tiles and other silicate-containing building materials, to prevent or minimize algal infestation that imparts a dark, unsightly appearance.[26]
A zinc-based plating layer formed by basic zinc chloride and magnesium has been shown to display excellent corrosion resistance.[27]
In color development materials
Basic zinc chloride is one of the three components to prepare color development materials used for pressure-sensitive copying papers and thermo-sensitive recording papers.[28][clarification needed]
References
- ^ a b "Simonkolleite" (PDF). Retrieved 2023-08-21.
- ^ a b "A to Z List".
- ^ a b c Hawthorne, F. C.; Sokolova, E. "Simonkolleite, Zn5(OH)8Cl2·H2O, a Decorated Interrupted-sheet Structure of the Form [Mφ2]4". The Canadian Mineralogist, 2002, 40, 939.
- ^ Zheng, L.; et al. "Corrosion behavior of pure zinc and its alloy under thin electrolyte layer". Acta Metall. Sin. (Engl. Lett.), 2010, 23(6), 416.
- ^ a b c Rasines, I.; Morales, J. I. "Thermal analysis of beta-Co2(OH)3Cl and Zn5(OH)8Cl2•(H2O)". Thermochimica Acta, 1980, 37, 239.
- ^ a b Garcia-Martinez, O. et al. "On the thermal decomposition of the zinc(II) hydroxide chlorides Zn5(OH)8Cl2•(H2O) and beta-Zn(OH)Cl". J. Mat. Sci. 1994, 29, 5429
- ^ a b Hoffman, J. W.; Lauder, I. "Basic zinc chloride". Aust. J. Chem. 1968, 21, 1439
- ^ Srivastava, O. K.; Secco, E. A. "Studies on metal hydroxy compounds. I. Thermal analyses of zinc derivatives e-Zn(OH)2, Zn5(OH)8Cl2•(H2O), beta-ZnOHCl, and ZnOHF." Can. J. Chem. 1967, 45, 579
- ^ http://www.micro.net/pdf/MicroNutrients%20TBZC%20MSDS%208-22-01.pdf[dead link]
- ^ a b Li, Y. et al. "Synthesis and characterization of simonkolleite nanodisks and their conversion into ZnO nanostructures". Cryst. Res. Technol. 2011, 1
- ^ Ostwald, H. R.; Feitknecht, W. Helv. Chim. Acta., 1961, 44, 847
- ^ Nowacki, W.; Silverman, J. H. Z. Kristallogr. 1961, 115, 21
- ^ a b Tanaka, H.; et al. "Synthesis and characterization of layered zinc hydroxychlorides". J. Solid State Chem. 2007, 180, 2061
- ^ a b c d Cao, J., P. R. Henry, C. B. Ammerman, R. D. Miles, and R. C. Littel. 2000. "Relative bioavailability of basic zinc sulfate and basic zinc chloride for chicks". J. Appl. Poultry Res. 9:513-517
- ^ a b c d Batal, A. B., T. M. Parr, and D. H. Baker. 2001. "Zinc bioavailability in tetrabasic zinc chloride and the dietary zinc requirement of young chicks fed a soy concentrate diet". Poultry Sci. 80:87-91
- ^ a b Edwards, H. M., III., and D. H. Baker. 2000. "Zinc bioavailability in soybean meal". J. Anim. Sci. 78:1017–1021
- ^ a b c Mavromichalis, I., D. M. Webel, E. N. Parr, and D. H. Baker. 2001. "Growth promoting efficacy of pharmacologic doses of tetrabasic zinc chloride in diets for nursery pigs". Can. J. Anim. Sci. 81:387–391
- ^ Hahn, J. D. and D. H. Baker. 1993. "Growth and plasma zinc responses of young pigs fed pharmacologic levels of zinc." J. Anim. Sci. 71:3020–3024
- ^ Hill, G. M., G. L. Cromwell, T. D. Crenshaw, C. R. Dove, R. C. Ewan, D. A. Knabe, A. J. Lewis, G. W. Libal, D. C. Mahan, G. C. Shurson, L. L. Southern, and T. L. Veuum. 2000. "Growth promotion effects and plasma changes from feeding high dietary concentrations of zinc and copper to weanling pigs (regional study)". J. Anim. Sci. 78:1010–1016
- ^ Hortin, A. E.; P. J. Bechtel and D. H. Baker. 1991. "Efficacy of pork loin as a source of zinc, and effect of added cysteine on zinc bioavailability." J. Food Sci. 56:1505–1508. Mavromichalis, I., C. M. Peter, T. M. Parr, D. Ganessunker, and D. H. Baker. 2000. "Growth promoting efficacy in young pigs of two sources of zinc oxide having either a high or a low bioavailability of zinc". J. Anim. Sci. 78:2896–2902
- ^ a b Zhang, B.; Guo, Y. "Beneficial effects of tetrabasic zinc chloride for weanling piglets and the bioavailability of zinc in tetrabasic form relative to ZnO". Animal Feed Science and Technology. 2007, 135, 75–85
- ^ a b Zhang, B.; Guo, Y. "Influence of tetrabasic zinc chloride and copper sulphate on growth performance and some physiological parameters in the digestive tract of weanling piglets". J. Animal and Feed Sciences, 2009, 18, 465–477
- ^ GB753251, 1956
- ^ Soparkar, C. WO2011005577A1
- ^ Gibbs, C. D.; Lyle, I. G.; Smith, R. G. GB2243775A, 1991
- ^ Lodge, J. R. US3998644, 1976
- ^ (a) Ferkous, H.; et al. "Investigation of the Ability of the Corrosion Protection of Zn-Mg Coatings". The Open Corrosion Journal, 2009, 2, 26–31. (b) Hiroshi, S.; et al. JP1312081A, 1989; JP3107469A, 1991
- ^ Osamu, F.; et al. JP55069494A