STUDY OF LABORATORY SCALE PREPARATION AND DEVELOPMENT OF A PROCESS FOR BARIUM PEROXIDE.
ABSTRACT: The objective of this research work was to develop a process for indigenous production of Barium peroxide. BaO2 can be prepared with commercially available barium carbonate in the presence of hydrogen peroxide. The material was analyzed for different parameters. The pH of the barium peroxide in water showed that it is basic in nature.BaO2 was insoluble in cold water but slightly soluble in hot water, soluble in conc. HCl with turbidity and completely soluble in conc. HNO3 . The optimum percentage yield was found to 93% for 0.1 M concentration of barium hydroxide and hydrogen peroxide. Different parameters such as temperature, pH, stirring speed and solubility were applied to the optimum yield. Barium was estimated gravimetrically in the sample solution as barium sulfate.
Its optimum percentage yield was 75.5%. Analysis for metals by atomic absorption spectroscopy showed 0.0041% chromium, 0.015% iron, 0.0315% magnesium, 0.0258% lead, 0.0044% calcium. The purity of barium peroxide was checked by KMnO4 titration. Purity of sample solution was determined up to 94.9%.
Keywords: Barium peroxide, Barium dioxide, Barium superoxide, Atomic-Absorption Spectrophotometer, Barium, BaO2
Barium peroxide is also called as Barium binoxide, Barium dioxide or Barium superoxide. The molecular weight of BaO2 is 169.33gms/mol. The percentage composition is as, Ba-81.12%, O2 - 18.88%. Barium peroxide has Tetragonal crystals. It is practically insoluble in water and dil. Acetic acid. It is made by precipitation of a reliable barium salt with oxygen is used in metal primers and as an ingredient of pyrotechnical composition. BaO2 is used for the detection of chromate and sulfate ions By ion precipitation as BaCrO4 and BaSO4. Barium peroxide arises by the reversible absorption of O2 by barium oxide. The oxygen is released above 500degC.
2 BaO + O2 - 2 BaO2
The grayish white ppt. of BaO2 is formed by reaction of barium salt solution and hydrogen peroxide solution BaO2 crystallizes as grayish white transparent tetragonal crystals which are isomorphous with barium sulfate, which also gives a vivid green color, as do all barium compounds. White or gray powder microstrip, in the air to absorb carbon dioxide emits oxygen generation barium carbonate, with the formation of acid salt and hydrogen peroxide. Contact with organic matter, friction or impact can cause a fire or explosion. It has 450degC melting point. Barium peroxide is an oxidizing agent, which is used for bleaching. It is used in fire works as an oxidizer, which also gives a vivid green color, as do all barium compounds .
Barytes is a grey powder, having a specific gravity of about 4. It has a caustic, alkaline taste; converts vegetable blues to greens, and neutralizes the strong other binary compounds of barium with the non-metallic elements are the peroxide, the chloride, the iodide (From the Phases of Matter)
Barium dioxide is used to make the germicide bleach, hydrogen peroxide. Barium monoxide is used in sugar refining. The most common barium ore is barite, a natural compound of barium, sulphur and oxygen.
The highly flammable mix contains 85 percent barium peroxide and 15 percent magnesium.
It is a strong oxidizer having many harmful impacts when contacts with other material, may cause fire. It may fatal if swallowed, Harmful if inhaled. It causes irritation to skin, eyes and respiratory tract. It affects muscles (including the heart) and central nervous system. On inhalation barium peroxide may cause irritation to the nose, throat, and respiratory tract. Symptoms may include sore throat, coughing, and shortness of breath. Systemic poisoning may occur in sensitive individuals with symptoms similar to those of ingestion. Ingestion may cause tightness of the muscles of the face and neck, vomiting, diarrhea, abdominal pain, muscular tremors, anxiety, weakness, labored breathing, cardiac irregularity, convulsions, and death from cardiac and respiratory failure. Estimated lethal dose lies between 1 to 15 grams. Skin Contact Causes irritation to skin. Symptoms include redness, itching, and pain. Eye contact causes irritation, redness and pain .
Barium peroxide can also be used in green tracer ammunition and as a bleaching agent, as an oxidizer in various ordnance and pyrotechnic mixtures, in Hair Dyes, for the processing of oxygen and hydrogen peroxide, in the welding industry, to bleach animal substances, vegetable fibers and straw, oxidizer in organic synthesis and as a catalyst to start an aluminothermic reaction
Table 1 Physical and Chemical Properties
Solubility###Practically insoluble and decomposes in water
Density###4.96 at 20C (68F)
PH###Alkaline in between 9-12.
Boiling Point###800C (1472F) Decomposes.
Melting Point###450C (842F)
Makarov S. Z. et al  found that data of thermal investigations with a recording pyrometer, and also investigations of the processes of decomposition of barium peroxide compounds, made it possible to establish the individuality of each of these compounds: BaO2, BaO2*8H2O, BaO2*H2O2, and BaO2*2H2O2.
Chatterjee R. and Dey Arun K.  used the ring oven method separate strontium and barium from calcium as sparingly soluble rhodizonate on filter paper discs. Douglas L.A et al  repoted that gas chromatographic investigations showed that the barium peroxide technique was not satisfactory for maintenance of aerobic conditions or for determination of carbon dioxide evolved during incubation of soils treated with organic materials. Till L.  explained that decomposition temperature of barium peroxide in equilibrium with the oxygen pressure in the gas phase had been determined by thermogravimetric measurements. Bakulina V. M. et al  in an x-ray study of ozonized barium peroxide revealed that the formation of solid solutions between barium peroxide and the superoxide was possible. Moneuse Carole et al  reported that molten barium hydroxide was used at 800degC as a catalyst for the oxidative coupling of methane.
Sangalov Yu. A. et al  in 2001 researched that the effect of mechanical treatment on the properties of barium peroxide-high-temperature source of oxygen was considered. Kireeva M. S et al  in 2002 found that data were presented on the structural properties, water solubility, and chemical reactivity of mechanically activated BaO2. Toribio P. P. et al  in 2005 researched that barium compounds (barium oxide, barium acetylacetonate, barium nitrate) had been used as catalysts for the liquid-phase oxidation of ethyl benzene with molecular oxygen. Ethylbenzene hydroperoxide (EBHP) was the major product, although small amounts of acetophenone (ACP) and 1-phenylethanol were also formed, indicating that C-H bond activation takes place only at the alkyl chain. Li Wei-Zhen et al  in 2009 did the Comparison of barium peroxide, Ba(OH)2 and Ba(NO3)2 as the precursor of BaO for the preparation of NO x -storage BaO/Al2O3 material was carried out.
Ho Park Jong et al  in 2010 studied that oxygen-selective adsorbents by two different methods, hydrothermal and sol-gel methods. The adsorption and desorption characteristics of these adsorbents were compared in terms of stability and sorption capacity.
Chen Li Chia et al.  in 2010 claimed that a highly hydroxylated barium titanate (BaTiO3) nanopowder had been prepared by oxidizing the BaTiO3 with an aqueous solution of hydrogen peroxide (H2O2). Busurina M. L. et al  in 2010 researched that the effect of a contactless electric field on the interactions involved in the combustion of the BaO2-Fe and MnO2-Fe systems. They found the possibility of increasing the extent of chemical conversion during the combustion of oxide systems by applying an external electric field. A possible mechanism of the influence of an electric field on the redox processes occurring during the combustion of oxide systems composed of a metal fuel and a solid oxidizer was described.
The objective of this study was to investigate the cheap and best process for lab. Scale production of Barium peroxide.
2. MATERIAL and METHODS
2.1 Atomic-Absorption Spectrophotometer
Concentration measurements are usually determined from a working curve after calibrating the instrument with standards of known concentration.
2.2 Method for Preparation of BaO2
There were several methods to prepare barium peroxide. But economically it was the cheapest way to prepare barium peroxide through barium carbonate.
The method can be divided into 3 steps. First of weighed about 54g of solid barium carbonate through electrical balance accurately and took it in 500mL beaker. Then added about 250mL distilled water in it and mixed it well. A suspended particle solution (slurry) was formed.53mL of conc. HCl was added in the slurry drop by drop. Gradually barium carbonate became soluble. Continuously check the pH of the solution and got neutral barium chloride solution which was clear, white, colorless solution along with carbon dioxide gas evolved. Now in 50mL beaker took 23g on NaOH pallets, added 50mL of distilled water to make solution. Now put this solution into barium chloride formed a milky white solution. then in third step 18g of H2O2(50%) was taken in 300mL beaker and added 250 ml distilled water to make dilute solution, was added in barium hydroxide milky white solution. precipitates of barium peroxide were formed which was filtered out. Washed the solution again and dried the crystals in the oven fig 1.
2.3 Analysis of BaO2
Qualitatively Barium was estimated by FLAME TEST. Upon burning BaO!2 !on flame, it gave non luminous barium with a pale apple green flame. All of the oxides are white, ionic, basic solids, which show the presence of Barium. Qualitatively Oxygen was estimated by IGNITION TEST. Apply a glowing splint or spill. It re-ignited to a flame). The relighted splint is mainly combustible carbon.
C (in wood) + O2 (g) - CO2 (g)
2.4 Quantitative Analysis of Barium
Barium was estimated quantitatively by methods of Atomic Absorption Spectrophotometer, Flame Emission Photometer, Gravimetric Method and Volumetric Method.
2.5 Purity Test
Weighed accurately about 0.0g of BaO2, added 30ml of distilled water and 25ml of 10% HCl and titrated with 0.1 N KMnO4 solutions. One mole of 1 N KMnO4 permanganate = 0.008468g BaO2/log 92778.
Dissolved 0.5g in 30mL water and 2ml of HNO3.filtered and dilute the filtrate to 100 ml to 20mL of filtrate added 1ml of AgNO3 the resulting turbidity is not more than in the blank to which 0.015mg of chloride has been added.
2.7 Calcium and alkalis 2 g salt was dissolved in 120ml water and 5ml of HCl. Heated the solution to boiling add 25ml of 10% H2SO4 and allow to stand overnight. Diluted the water with 150mL mix and filter. Evaporate 75ml of filtrate and ignite. The residue does not exceed 0.007g.
2.8 Estimation of Barium as Barium sulphate
The solution (100ml) contained 0.15 g of barium, less than 1% by volume of conc. HCl. While boiling, a slight excess of hot N-Sulphuric acid slowly added with constant stirring. Digested on steam bath until the precipitate settled t, filtered, washed out with hot water containing two drops of sulphuric acid per liter, and then with a little water until the acid was removed and weighed as barium sulphate.
2.9 Preparation of Barium Peroxide Using 0.1, 0.3, 0.5, 1.0 and 1.5 M BaOH Solutions without Washing
To make a homogeneous solution of barium hydroxide in water, 0.1734, 0.51402, 0.8567, 1.7134 and 2.5701g of barium hydroxide was added in 500ml beakers marked as B1, B2, B3, B4 and B5 separately, each containing 100ml of de-ionized water. Each of the mixture was then stirred for five minutes at the speed of 50rpm to ensure homogeneity.
As above, to another batch of 500ml beakers marked as B@1, B@2, B@3, B@4 and B@5 , containing 100 ml of de-ionized water , The volume 0.03401, 0.10203, 0.17005, 0.3401 and 0.51015 ml of hydrogen peroxide were added followed by stirring for five to ten minute at the speed of 100rpm to get homogeneous solution. Then kept it for the precipitation reaction took place until grey-white precipitate of barium peroxide settled down. It was then filtered with the help of gooch crucible and the filtered out ppt. was then put into electric oven. The %age yield was calculated with following formula.
Percetage yield of Barium = ------------###x 100
2.10 Preparation of Barium Peroxide Using 0.1, 0.3, 0.5, 1.0 and 1.5M
BaO2 with Washing
In another batch BaO2 was prepared with the same method as described above. But this time BaO2 after drying in the electric oven was given 5 washings with distilled water and then filtered precipitates were dried in oven at the temperature i. e. 100oC for 65 minutes. The %age yield was also calculated as shown in fig 3. Fig 4 shows the flow Sheet diagram for the preparation of BaO2 after washing.
2.11 Effect of Temperature on Percentage Yield of Barium Peroxide
To investigate the effect of temperature on yield of barium peroxide prepared 0.1M solution of barium peroxide, diluted to 200ml distilled water and divided into five equal parts. The temperature was maintained as 40OC, 50oC, 60oC, 70oC, and 80oC respectively. The stirring speed was kept constant and the percentage yield was thus calculated.
2.12 Effect of Stirring Speed on Percentage Yield of Barium Peroxide
To investigate effect of the stirring speed on yield of barium peroxide, 0.1M solution of barium peroxide was and diluted to 200ml distelled water and divided into five equal parts, the stirring speed was maintained as, 20rpm, 30rpm, 40rpm, 50rpm, 60rpm respectively, the temperature also was kept constant and the percentage yield was calculated.
2.13 Effect of pH on Percentage Yield of Barium Peroxide
To investigate the effect of pH on yield of b barium peroxide prepared 0.1M solution of barium peroxide and diluted to 200mL with distilled water and divided into five equal parts, the stirring speed and the temperature were also kept constant and the percentage yield was calculated.
2.14 Solubility Behavior of Barium Peroxide in different solvents
Solubility Behavior of Barium Peroxide in different solvents was checked and evaluated i. e. Water, Acetic Acid, Hydrochloric Acid, Sulphuric Acid and Nitric Acid.
2.15 Solubility Behavior of BaO2 in Different Percentage Solutions of HNO3
To check out the solubility behavior of barium peroxide in different percent solution of nitric acid prepared 2,4,6,8,10% solutions of HNO3 respectively and dissolved the barium peroxide in each solutions until the no more amount of barium peroxide dissolved in hot solution. After each completion of step, pH of solution was noted.
3. RESULTS AND DISCUSSION
3.1 Percentage Composition (By weight) of Barium Peroxide
Percentage of Ba and O in BaO2 was calculated to be 81.12% Ba and 18.88 % O2 as shown in the pie chart 1.
The percentage yield of bariun peroxide without washing is shown in fig 2 which shows the maximum yield at 0.1M Ba (OH)2 solution and 0.1M H2O2 solution. The maximum percentage was found to be 97% that deceased with increase in the molarity of both solutions. Minimum amount of BaO2 achieved at higher molarity i. e. 82% when 1.5 M BaOH and H2O2 solutions were used. Total amount of BaO2 achieved was 2.09 g.
The fig 3 shows the percentage yield of barium peroxide with washings. It is clear that percentage of yield goes on decreasing with increase in the molarity (0.1 to 1.5M) of the reacting components. We conclude that low Molarity (0.1M)of the BaOH and H2O2 is optimum for maximumyield of BaO2. Flow sheet diagram of preparation of BeO2 is sin fig 4. The effect of temperature on percentage yield at constant stirring had been shown in fig 5 which shows that yield is higher at low temperature i. e. 99% at 40 @C and 71% at 80 @C. The optimal temperature was found to be 40@C. The effect of stirring speed on percentage yield at constant stirring is given in fig 6. Maximum yield of BaO2 was noted at the speed of 20rpm which was 96%. With increase in agitation from 20 rpm to 80 rpm, yield was different concentrations of HNO3 (2, 4, 6, 8 and10%) had been shown in Fig 8, with increase of concentration of HNO3 solubility of BaO2 was increased gradually and maximum solubility 9.91g/100 ml was achieved in 10% HNO3.
The solubility behavior of BaO2 in different solvents had been shown in Table 2. BaO2 is sparingly soluble in water and acetic acid. It is slightly soluble in cold state in the HCl, H2SO4, and HNO3. BaO2 is readily soluble in cold state in the HCl, H2SO4, and HNO3.
Table 2 Solubility Effect of BaO2
In every aspect###In every aspect###In warm condition###In warm condition###In warm condition
This study gives us a simple, less expensive and industrially viable method to prepare barium peroxide which has very important industrial applications. It is concluded from the experimental work regarding the properties of BaO2 that optimum percentage yield 95% of BaO2 can be obtained from 0.1 M barium hydroxide and hydrogen peroxide at pH 7, temperature 25oC without stirring, without washing. The optimum percentage yield 93% of BaO2 can be obtained from 0.1 M barium hydroxide and hydrogen peroxide at pH 7, temperature 25oC without stirring, with washing. The maximum %age yield can be obtained at low temperature e. g. At 40oC the %age yield of BaO2 was 99% and at high temperature 80oC the yield was minimum i.e. 71%. By increasing the stirring speed the %age yield decreases e.g.when the stirring speed was 20 Rpm the yield was 96% and when stirring speed was 80 Rpm the yield was 92%.
Author is thank full to Higher Education Commision (HEC) , Govt. of Pakistan and Edocation Deptt., Government of Punjab Lahore.
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Department of Chemistry, Government Islamia Post Graduate College Gujranwala, Pakistan
Division of Science and Technology, University of Education, Township campus, Lahore, Pakistan
Pakistan Council of Scientific and Industrial Research (PCSIR), Lahore-54590, Pakistan
Institute of Biochemistry and Biotechnology, Punjab University, Lahore, Pakistan
Institute of Chemistry, University of the Punjab, Lahore-54590, Pakistan
(Corresponding Author: E-mail: email@example.com, Cell # +92-300-7432748)
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|Author:||Khokhar, Zia-ullah; Riaz, Faiza; Ahmad, Sh. Asrar; Manzoor, Asma; Mahmood, Khalid; Gulzar, Asad; Tip|
|Date:||Dec 31, 2011|
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