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In the explanation of the sulfur cycle, it is often said that sulfur moves from the atmosphere to the ground by acid rain in the form of sulfuric acid. Can plants directly use sulfuric acid to assimilate sulfur?
Plants have sulfate transporters which they use to assimilate sulfur. Since sulfate is the conjugate base of sulfuric acid, this could be construed as a "yes" for your question. Sulfuric acid would be present in its conjugate base form at physiological pH values.
However, it would be unwise to water your plants with sulfuric acid, as many plants have an optimal pH range which will quickly cause death when sulfuric acid lowers the pH of the soil below that range. As a result, areas afflicted by acid rain may require treatment with alkaline limestone to resolve this issue.
Sulfuric Acid
Sulfuric acid (H2S04) is a corrosive substance, destructive to the skin, eyes, teeth, and lungs. Severe exposure can result in death. Workers may be harmed from exposure to sulfuric acid. The level of exposure depends on dose, duration, and type of work being done.
Sulfuric acid is used in many industries. It&rsquos used to produce other chemicals, explosives and glue to refine petroleum to cure metal and in lead-based car batteries. Some examples of workers at risk of being exposed to sulfuric acid include the following:
- Outdoor workers who work in areas where coal, oil, or gas are burned
- Mechanics who handle dirty batteries
- Plumbers and contractors who come in contact with toilet bowl cleaners mixed with water
- Workers in publishing, printing or photography shops
- Fire fighters and steelworkers who are exposed to acid mists
NIOSH recommends that employers use the Hierarchy of Controls to prevent or reduce worker exposures. If you work in an industry that uses sulfuric acid, read chemical labels and the accompanying Safety Data Sheet for hazard information. Visit NIOSH&rsquos page on Managing Chemical Safety in the Workplace to learn more about controlling chemical workplace exposures.
The following resources provide information about occupational exposure to sulfuric acid. Useful search terms for sulfuric acid include &ldquobattery acid,&rdquo &ldquohydrogen sulfate,&rdquo &ldquooil of vitriol,&rdquo and &ldquosulfuric acid (aqueous).&rdquo
NIOSH Chemical Resources
The NIOSH Pocket Guide to Chemical Hazards (NPG) helps workers, employers, and occupational health professionals recognize and control workplace chemical hazards.
The NIOSH Manual of Analytical Methods (NMAM) is a collection of methods for sampling and analysis of contaminants in workplace air, and in the blood and urine of workers who are occupationally exposed.
The Health Hazard Evaluation Program (HHE) conducts onsite investigations of possible worker exposure to chemicals. Search the HHE database for more information on chemical topics.
This is a straightforward question with a not very straightforward answer. Acid rain and plant damage go hand in hand in areas prone to this type of pollution, but the changes to a plant’s environment and tissues are gradual. Eventually, a plant exposed to acid rain will die, but unless your plants are incredibly sensitive, the acid rain unusually potent and frequent or you’re a very bad gardener, the damage is not fatal.
The way that acid rain damages plants is very subtle. Over time, the acidic water alters the pH of the soil where your plants are growing, binding and dissolving vital minerals and carrying them away. As the soil pH falls, your plants will suffer increasingly obvious symptoms, including yellowing between the veins on their leaves.
Rain that falls on leaves can eat away the outer waxy layer of tissue that protects the plant from drying out, leading to the destruction of the chloroplasts that drive photosynthesis. When a lot of leaves are damaged at once, your plant may become very stressed and attract a host of pests and diseases organisms.
Effects of Different Treatments on Seed Germination Improvement of Calotropis persica
The purpose of this study was to investigate the effects of different treatments on seed germination in the desert plant species Calotropis persica (Gand.). This species is known to have long time for seed germination considering arid region condition and short time of access moist. An experiment was performed with 13 treatments and 4 replications in a completely randomized design. Treatments included KNO3 with concentrations of 0.1, 0.2, and 0.3 percent, immersion in hot water for five min, acetylsalicylic acid 100, 200, and 300 mg L −1 , ethereal sulfuric acid (60%) for 5 and 10 min, thiourea with concentrations of 0.1% and 0.3%, and prechilling for 10 days. Tap water was used as the control. Our findings indicate that KNO3 0.1% and 100 mg L −1 acetylsalicylic acid were the most effective treatments for improvement of seed germination properties in this species. In a comparison of the two mentioned treatment, KNO3 0.1% treatments is the best.
1. Introduction
Germination is a critical stage in the life cycle of weeds and crop plants and often controls population dynamics, with major practical implications. Seed germination is the critical stage for species survival [1, 2]. In recent 20 years, desertification has been recognized as a major environmental problem and is a major focus of United Nations Environment Programme [3]. Vegetation is a protector of the soil against water and wind erosion as well as a casualty of soil erosion [4, 5]. Each desert-inhabiting plant has its own complex of strategies that enables it to persist in desert habitats [6]. Strategies for improving the growth and development of arid region plant species have been investigated for many years. Treated seeds with chemical compound usually would exhibit rapid germination when absorbing water under field conditions [7].
Calotropis is a genus of flowering plants in the dogbane family, Apocynaceae. They are commonly known as milkweeds because of the latex they produce. Calotropis species are considered common weeds in some parts of the world. The flowers are fragrant and are often used in making floral tassels in some mainland Southeast Asian cultures. Calotropis persica is growing in tropical region only. Iran is a country in the mid-latitude belt of arid and semiarid regions of the Earth. Approximately 60% of Iran is classified as arid and semiarid [8]. Based on results, the seed of full ripening fruits with scarification had the highest germination percent. [9] investigated the effects of salt stress and prime on germination improvement and seedling growth of Calotropis procera L. seeds and the results showed that priming improved the seedling characteristics in all samples, especially in −0.05 MPa, but a decrease with decrease in osmotic potential. The work in [10] studied the effect of temperature, light, pretreatment, and storage on seed germination of Rhodomyrtus tomentosa and their result showed that light significantly improved germination of fresh seeds but storage decreased the light-sensitivity of germination. Soaking for 24 hours in 250–600 mg L −1 gibberellic acid, 5–20% potassium nitrate, or 10% hydrogen peroxide solution increased seed germination. Calotropis sp. is an important economic plant used for drug and other purposes. The purpose of this study was to develop methods to increase germination percentage, shorten germination time, provide more rate germination, and result in more efficient seed propagation techniques for C. persica seeds.
2. Material and Methods
Seeds of C. persica were collected from Jiroft arid regions in southern Iran in 2013. A preliminary germination test was performed and low germination percentage was obtained. To solve this problem, we implemented an experiment with a randomized complete design. Before the start of experiment, seeds were surface sterilized in 1% sodium hypochlorite solution for 5 min, then rinsed with sterilized water, and air-dried for 28 h before putting in petri dishes. Treatments included pretreatment with KNO3 (0.1 and 0.3 percent) for 48 hours, acetylsalicylic acid to the moisture in the petri dish (100, 200 and 100 mg L −1 ), prechilling (4 degrees centigrade for 10 days), hot water (70°C) for 5 min, ethereal sulfuric acid (60%) for 5 and 10 min, thiourea with concentrations of 0.1% and 0.3%, and control treatment (irrigation with distilled water). The seeds were placed on top of Whatman paper number 1 within 10 cm petri dishes containing 10 mL distilled water. Counting number of germinating seeds began from the first day and was done till the end of the experiment (19 days). Germination percentage was recorded daily during the study period. Rate of germination was estimated using modified Timpson’s index of germination velocity [11]. Mean germination time (MGT) was calculated to assess the rate of germination [12]:
where is the number of seeds which in day grow, the total number of seeds grown, and the number of days from the date of germination and the germination rate index was obtained by reversing MGT at the end of this period final germination percentage was recorded. There are no outliers normality of data was checked and nonnormal data transformed by arc sin to verification of this hypothesis arc sin transformation was used for germination percentage before analysis [13]. Experimental data was analyzed by SPSS 17.0 to analyze the data and Duncan’s test at 5% level was used to compare the means.
3. Results
The results of ANOVA (Table 1) showed that there are significant differences (at 1% level) between effective treatments on germination characteristics and the different treatments resulted in significant differences among germination properties (Table 1).
The results of this research showed that germination percentage of C. persica increases due to application of KNO3 in different concentrations and acetylsalicylic acid 100 and 200 mg L −1 and decreased germination percentage due to application of hot water for 5 min, prechilling for 10 days, sulfuric acid 5 and 10 min, and thiourea 0.3%. Acetylsalicylic acid 300 mg L −1 and thiourea 0.1% have the same effect on germination percentage in comparison to control treatment. The increased germination percentage by KNO3 0.1, 0.2, and 0.3% and acetylsalicylic acid 100 mg L −1 was significant (Figure 1).
The seed germination rates of C. persica increased significantly when KNO3 0.1% was used. Acetylsalicylic acid 200 and 300 mg L −1 and thiourea 0.3% increased seed germination rate, but this increase was not significant. However, the germination rate was decreased when hot water for 5 min, prechilling for 10 days, sulfuric acid for 5 and 10 min, KNO3 0.2 and 0.3%, acetylsalicylic acid 100 mg L −1 , and thiourea 0.3% were used (Figure 2).
Mean germination time of C. persica decreased by using KNO3 0.1% but this difference was not significant. In seeds of C. persica, all treatments, except for KNO3 0.1%, caused increase in mean germination time (Figure 3).
4. Discussion and Conclusion
According to the obtained results, KNO3 0.1% and acetylsalicylic acid 100 mg L −1 were the most effective treatments for improvement of seed germination properties in C. persica plant species. In a comparison of the two mentioned treatments, KNO3 0.1% treatment is the best. This technique has become a common seed treatment that can increase rate, percentage, and uniformity of germination or seedling emergence, mainly under unfavorable environmental conditions. Rapid seed germination and stand establishment are critical factors for crop production under stress conditions. Hot water for 5 min and prechilling for 10 days did not show positive effect on germination improvement. The study result of scarification of seeds of Acacia angustissima showed that seeds soaking in hot water cause seed germination induction but increasing duration of seed contact with hot water leads to decline of seed germination percentage [14]. In a research it is shown that prechilling for 10 days had a positive effect on germination rate and mean germination time of both medicinal species of Foeniculum vulgare and Cuscuta epithymum but germination percentage decreased due to application of prechilling [15]. Sulfuric acid for 5 and 10 min did not have positive effect on seed germination of C. persica as a result, seed treatment with sulfuric acid cannot improve seed germination. This result demonstrated that above mentioned treatment had the destructive effect on embryo. It is notified that increasing in doses of sulfuric acid caused germination improvement and suggested chemical scarification in concentrated H2SO4 for 2 hours [16]. In this research thiourea did not have a positive effect on germination improvement of C. persica. Acetylsalicylic acid 100 mg L −1 improved mean germination time and germination percentage in comparison with amount of 200 and 300 mg L −1 .
In this research, KNO3 0.1% is recognized as the best treatment for improvement seed germination properties of C. persica. Similar results were reported in previous studies for the species of Citrullus colocynthis [17], Foeniculum vulgare and Cuscuta epithymum [15], Hypericum aviculariifolium [18], and Avena fatua [19]. According these results, KNO3 0.1% treatment is suggested for improvement of C. persica germination and this treatment is proper for propagation of studied species. Positive effect of KNO3 could be due to its role in balancing hormonal portion within seed which in turn results in germination inhibitors ratio like ABA. (abscisic acid). Virtually all of the cellular and metabolic events that are known to occur before the completion of germination of nondormant seeds also occur in imbibed dormant seeds indeed, the metabolic activities of the latter are frequently only subtly different from those of the former [20]. The seeds of most Mediterranean and desert species have dormancy characteristics or structural properties that prevent immediate germination of at least a proportion of the seeds [21–24]. The results obtained will be useful in carrying out tree improvement and plantings of C. persica trees for fuel wood, local medicine, and industrial production. Rapid seedling growth is also essential for reclamation of desert. This information could ultimately help in the sustainable development of the arid zones.
Conflict of Interests
The authors declare that there is no conflict of interests regarding the publication of this paper.
Acknowledgments
This research was supported by Iranian Revolutionary Guards Navy. The authors would like to thank Hamid Reza Ahmadinia Ph.D. student of Fishery in Gorgan University of Agriculture and Natural Resources for his help with the creation of this work.
References
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Copyright
Copyright © 2014 Asghar Farajollahi et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Sulfur bacterium
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Sulfur bacterium, plural Sulfur Bacteria, any of a diverse group of microorganisms capable of metabolizing sulfur and its compounds and important in the sulfur cycle (q.v.) in nature. Some of the common sulfur substances that are used by these bacteria as an energy source are hydrogen sulfide (H2S), sulfur, and thiosulfate (S2O3 2- ). The final product of sulfur oxidation is sulfate (SO4 2- ).
Thiobacillus, widespread in marine and terrestrial habitats, oxidizes sulfur, producing sulfates useful to plants in deep ground deposits it generates sulfuric acid, which dissolves metals in mines but also corrodes concrete and steel. Desulfovibrio desulficans reduces sulfates in waterlogged soils and sewage to hydrogen sulfide, a gas with the rotten egg odour so common to such places. Thiothrix, common in sulfur springs and in sewage, and Sulfolobus, confined to sulfur-rich hot springs, transform hydrogen sulfide to elemental sulfur.
Many species in the families Chromatiaceae (purple sulfur bacteria) and Chlorobiaceae (green sulfur bacteria) utilize energy from light in an oxygen-free environment to transform sulfur and its compounds to sulfates.
Sulfuric acid
Table (1.2.1): physical properties1
Sulfuric acid is a very important chemical commodity, and indeed, a nation’s sulfuric acid production is a good indicator of its industrial strength.
It is used as electrolyte in lead-acid batteries (accumulators) .
It is important in the production of fertilizers such as ammonium sulfate (sulfate of ammonia), (NH4)2SO4, and superphosphate, Ca(H2PO4)2, which is formed when rock phosphate is treated with sulfuric acid.
It is used to remove oxides from iron and steel before galvanising or electroplating .
Concentrated sulfuric acid is used as a dehydrating agent, that is, to remove water, since it has a tendency to form hydrates such as H2SO4.H2O, H2SO4.2H2O.
Sulfuric acid is used in the production of nitroglycerine, an inorganic ester & organic nitrate, which is used as an explosive.
It is used in petroleum refining to wash impurities out of gasoline and other refinery products.
It is used in manufacturing of hydrochloric acid, nitric acid, phosphoric acid, ether, plastics, metal sulfates, cellophane, dyes, drugs, perfumes, disinfectants and even glue.1
This chart shows the distribution of using sulfuric acid
Figure (1.3.1): Sulfuric Acid Distribution.1
Specification of raw materials
Yellow colored lumps, crystals, powder, or formed shape
Lumps 75-115 lbs./ft3 Powder 33-80 lbs./ft3
388.36 K, 115.21 °C, 239.38 °F
717.8 K, 444.6 °C, 832.3 °F
Table (1.3.1): Physical & Chemical Properties of Sulfur.1
2.1 History and Current processes
The discovery of sulfuric acid is credited to the 8th century chemist and alchemist, Jabir ibn Hayyan (Geber). The acid was later studied by 9th century Persian physician and alchemist Ibn Zakariya al-Razi (Rhazes), who obtained the substance by dry distillation of minerals including iron(II) sulfate heptahydrate, FeSO4·7H2O, and copper(II) sulfate pentahydrate, CuSO4·5H2O. When heated, these compounds decompose to iron(II) oxide and copper(II) oxide, respectively, giving off water and sulfur trioxide, which combine to produce a dilute solution of sulfuric acid. 1
This method was popularized in Europe through translations of Arabic and Persian treatises, as well as books by European alchemists, such as the 13th-century German Albertus Magnus.1
There are two major processes (lead chamber and contact) for production of sulfuric acid and it is available commercially in a number of grades and concentrations. The lead chamber process, the older of the two processes, is used to produce much of the acid used to make fertilizers it produces a relatively dilute acid (62%-78% H2SO4). The contact process produces a purer, more concentrated acid but requires purer raw materials and the use of expensive catalysts. n both processes sulfur dioxide is oxidized and dissolved in water. The sulfur dioxide is obtained by burning sulfur, by burning pyrites (iron sulfides), by roasting nonferrous sulfide ores preparatory to smelting, or by burning hydrogen sulfide gas. Some sulfuric acid is also made from ferrous sulfate waste solutions from pickling iron and steel and from waste acid sludge from oil refineries. 1
This table shows the production rates of sulfuric acid (in metric tones) in some countries at different years.
Production of sulfuric acid in metric tones
Table (2.2.1): Production Rates of Sulfuric Acid.3
This table shows the production and sales amounts of sulfuric acid and the consumption rate of sulfur in Jordan from 2000 to 2005, these amounts in (ton/year).
Table (2.2.2)Jordan Production, Sales and Raw Material Consumption.5
2.3 Prices trends of the raw material and product
The global sulfuric acid market experienced an unprecedented rise and fall in pricing between fall 2007 and spring 2009. Consumption of sulfuric acid for fertilizers fell steeply in the second half of 2008 due to the collapse in the global economy. The second half of 2009 is expected to experience almost flat to slightly positive growth, anticipating the improvement in market conditions in 2010. Trade is expected to fall globally, except for Southeast Asia, which would continue to depend on imports. As of early spring 2009, the market is continuing to deteriorate as the supply shortage situation has been replaced by product oversupply in almost all regions.
And the world sulfuric acid supply trends are shown in the following chart.
Figure (2.3.1): World Sulfuric Acid Supply.2
Sulfuric acid is an important raw material used in many industrial processes, such as phosphate fertilizer production and to a much lesser extent for nitrogen and potassium fertilizers, sulfuric acid is produced by catalytic oxidation of sulfur dioxide to sulfur trioxide, which is subsequently absorbed in water to form sulfuric acid.
There are no major variations of commercial interests on this mentioned chemistry. There are alternatives as to source of Sulfur dioxide and method of conversion to sulfur trioxide. The two most common methods for the conversion of sulfur dioxide to sulfuric
This is an old process and was introduced in Europe in near the middle of 18th century, it’s used to produce much of the acid used to make fertilizers it produces a- relatively dilute acid (62%-78% H2SO4).The classic lead chamber process consists of three stages: Glover tower, lead chambers and Guy-Lussac Tower.
In this method hot sulfuric dioxide gas enters the bottom of the reactor called a Glover tower where it is washed with nitrous vitriol (sulfuric acid with nitric oxide, NO, and nitrogen dioxide, NO2, dissolved in it) and mixed with nitric oxide and nitrogen dioxide gases.
The Glover tower serves two functions: concentration of the chamber acid and stripping of nitrogen oxides from the liquid to the gas. Concentration of the chamber acid (62% to 68% H2SO4) is achieved by the hot gases entering the tower which evaporate water from the acid.
Some of the sulfur dioxide is oxidized to sulfur trioxide and dissolved in the acid wash to form tower acid or Glover acid (about 78% H2SO4). The dissolved nitrogen oxides are stripped from the acid and carried with the gas out of the Glover tower into the lead chambers.
From the acid tower a mixture of gases (including sulfur dioxide and trioxide, nitrogen oxides, nitrogen, oxygen, and steam) is transferred to a lead-lined chamber where it is reacted with more water.
Sulfuric acid is formed by a complex series of reactions it condenses on the walls and collects on the floor of the chamber. There may be from three to twelve chambers in a series. The acid produced in the chambers, often called chamber acid or fertilizer acid, contains 62% to 68% H2SO4.
After the gases have passed through the chambers they are passed into a reactor called the Gay-Lussac tower where they are washed with cooled concentrated acid (from the acid tower) the nitrogen oxides and unreacted sulfur dioxide dissolve in the acid to form the nitrous vitriol used in the acid tower. Remaining waste gases are usually discharged into the atmosphere.
Product acid at a concentration of 78% H2SO4 is drawn from the cooled acid stream that is circulated from the Glover tower to the Guy-Lussac tower. Nitrogen losses are made up with nitric acid which is added to the Glover tower.
The major disadvantage includes the limitations in throughput, quality and concentration of the acid produced, also the environmental pollution.
Figure (3.1.1): Typical process flow sheet for the lead Chamber.
Because of economic reasons Contact plants are widely used compared to the lead plants, they are classified according to the raw materials charged to them: elemental Sulfur burning, spent sulfuric acid and hydrogen sulfide burning, and metal sulfide ores and smelter gas burning. The contributions from these plants to the total acid production are 81, 8, and 11 percent, respectively.
The contact process incorporates three basic operations (stages), each of which corresponds to a distinct chemical reaction.
First, elemental sulfur is received in a solid form containing various impurities. The sulfur is melted in the sulfur melter in the presence of hydrated lime which neutralizes any acidity present in the sulfur. This neutralization prevents problems of acid corrosion which would otherwise be encountered.
Heat for the melting of the sulfur is supplied from steam coils. The molten sulfur is kept agitated to improve heat transfer, to prevent solids settling on the bottom of the sulfur pits and to prevent a crust forming on top. The “dirty sulfur” is filtered to remove impurities present and after filtering is transferred to the “clean sulfur” pit where it is kept molten until it is pumped to the burner.
Molten sulfur at a temperature of 130°C is sprayed into the burner in the presence of warm, dry air. The sulfur burns, forming sulfur dioxide
S + O2 € € € € SO2 ∆H = -300 kJ mol-1
The resulting sulfur dioxide is fed to a process unit called a converter, where it is catalytically oxidized to sulfur trioxide (SO3):
2SO2 + O2 € € € € 2SO3 ÃŽâ€H = -100 kJ mol-1
It’s apparent that the equation gives a decrease in volume this reaction would be aided by pressure. High conversions are however, obtainable with catalysts at 400 to 500oC with a small excess of oxygen and the use of pressure.
The available methods to maximize the formation of SO3:
As this is an exothermic process, a decrease in temperature by removal of the heat will favour the formation of SO3.
Increased oxygen concentration.
SO3 removal (as in the case of the double absorption process).
Catalyst selection, to reduce the working temperature (equilibrium).
In the contact processes, the sulfur dioxide is converted to sulfur trioxide by the use of metal oxide catalyst, the characteristics of the used catalyst are:
Porous carrier having large surface area, controlled pore size and resistance to process gases at high temperature in pellet form if used in fixed bed and
powdered form if used for fluidized bed. Ex- Alumina, silica gel, zeolites.
Preparations are generally kept secret for the competitive reasons but they usually
consist of adding water soluble compounds to gels or porous substrates and firing
at temperature below the sintering point.
Alkali and/or metallic compounds added in trace amounts to enhance the activity
A catalyst, vanadium pentoxide (V2O5) is used to increase the reaction rate because it’s relatively immune to poisons, also because of its low initial investment and only 5% replacement per year. It is only effective above its melting point of 400 °C. The greatest conversion of SO2 to SO3 is reached by passing the gas over several catalyst beds, cooling the gas between each pass so that the reaction temperature remains between 400 and 500 °C. As can be seen the figure.
The disadvantages of using the V2O5 catalyst are that it must use dilute SO2 input (7-10%), as a catalyst it is less active and requires high oxygen or sulfur dioxide to give economic conversions also it requires larger converters and thus higher initial investment.
Finally, the sulfur trioxide is absorbed in to very concentrated sulfuric acid (a 98-99 percent solution of H2SO4 in water), This operation takes place in the absorbing tower where the gas travels up through the tower, counter-current to the acid falling from the top of the tower producing a thick fuming liquid called oleum, the oleum is mixed carefully with water to avoid producing fine mist of sulfuric acid that is difficult to condense and could escape to pollute the air, the sulfur trioxide in the oleum reacts with the water as follows:
SO3 + H2O € € € € € € € € H2SO4 ∆H = -200 kJ mol-1
It is clear that the reaction is exothermic and the absorbing sulfuric acid has to be cooled continuously the heat is available at a relatively low temperature and is not worth recovering.
The efficiency of the absorption step is related to :
The H2SO4 concentration of the absorbing liquid. (98.5 – 99.5%).
The temperature range of the liquid (normally 70 -120 0C).
The technique of the acid distribution.
The raw gas humidity (mist passes the absorption equipment).
The temperature of incoming gas.
The co-current or countercurrent character of the gas stream in the absorbing liquid.
Main disadvantages of the contact process are that concentrated acid (98%) of high purity can be produced directly and that compact plants of quite high capacity have now become rather common place.
The contact process can be applied in different techniques three of those techniques are described in the following sections
3.2.1 Single contact / single absorption process
After purification and drying, the SO2 is converted to SO3 using a series of four catalyst beds, containing alkali and V2O5. Afterwards, the SO3 is absorbed in concentrated sulfuric acid and, if necessary, an oleum absorber is installed upstream. SO3 reacts with the water contained in the absorber acid to yield H2SO4. The absorber acid is kept at the desired concentration of approximately 99% w/w by addition of water or dilute H2SO4.
The single contact/single absorption process is generally used for gases with an SO2 Content from 3 – 6 %. New single contact plants are built only for inlet gases with substantial fluctuation of the SO2 content.
The investment cost of this technique is low compared to the investment cost of double contact plants.
Figure (3.2.1.1): Typical process flow sheet for a single catalysis plant.
3.2.2 Double Contact/ Double Absorption Process
The double contact process was implemented to develop the single contact/single absorption process. In this process a primary SO2 conversion of 85 – 95 % is achieved in the first catalysis stage of the converter before entry into an intermediate absorber, depending on the arrangement of the converter beds and the contact time.
What makes the double contact/double absorption process more advantageous is that its ability to feed gases with higher SO2 concentrations than would be possible with the single catalysis process. Which leads to smaller gas volumes and therefore smaller equipment with comparable production capacities.
This results in a considerably higher conversion rate, if the residual gas is passed through the following converter beds (usually one or two). The SO3 which is formed in the second catalysis stage is absorbed in the final absorber.
In general the process uses gases with an SO2 content of 10 t o11 %. The inlet gas temperature is about 4000C. Gases with lower temperatures require reheating from 50 to 4000C. This is usually carried out with recovered heats from the conversion process.
Operating the double contact process at an elevated pressure of 5 bar increases the conversion rate by shifting the conversion equilibrium and favouring the formation of SO3.
The disadvantages are higher electricity consumption and, at the same time, less steam production. Higher NOx emissions are caused by higher sulfur combustion temperatures (18000C), but savings of 10 -17 % on investment costs are gained.
Figure 3.2.2.1: Typical process flow sheet for a sulfur burning double catalysis
3.2.3 Wet catalysis process
The wet catalysis process is applicable to wet SO2 gases. The potential for the formation of sulfuric acid mist might require tail gas treatment.
Wet SO2 gases (eg. from the burning of H2S gases or from the catalytic conversion of H2S gases) are directly supplied into the contact tower without previous drying. SO3 formed by the catalytic conversion immediately reacts with the moisture of the gases, thereby forming the acetic acid. The sulfuric acid is condensed in a condenser installed after the contact tower.
Sulfuric Acid Production By Lead Chamber process
Sulfuric Acid Production By single contact/single absorption process
Sulfuric Acid Production By double contact/double absorption process
Sulfuric Acid Production By Wet Catalysis process
Health and safety hazards involved
Less safe, waste gases are discharged to the atmosphere
Less amount of SO3 is absorbed so the rest is discharged to the atmosphere
A larger amount of SO3 is absorbed
A larger amount of SO3 is absorbed
Melted sulfur, H2O, O2, SO2, SO3.
Waste products and by products
Exhaust gases are discharged to the atmosphere
Large amounts of SO2 gas are discharged to the atmosphere
Less amounts of SO2 gas are discharged to the atmosphere, less heat released after each successive catalyst bed.
A larger amount of SO3 is absorbed
Acid Tower (Glover Tower), Lead Chambers, Reactor (Gay-lussac Tower)
Air dryer, burner, waste heat boiler, converter, single absorption column.
Air dryer, burner, waste heat boiler, converter, intermediate and external absorption column.
Contents
Grades of sulfuric acid Edit
Although nearly 100% sulfuric acid solutions can be made, the subsequent loss of SO
3 at the boiling point brings the concentration to 98.3% acid. The 98.3% grade is more stable in storage, and is the usual form of what is described as "concentrated sulfuric acid". Other concentrations are used for different purposes. Some common concentrations are: [12] [13]
Mass fraction H2SO4 | Density (kg/L) | Concentration (mol/L) | Common name |
---|---|---|---|
<29% | 1.00-1.25 | <4.2 | diluted sulfuric acid |
29–32% | 1.25–1.28 | 4.2–5.0 | battery acid (used in lead–acid batteries) |
62–70% | 1.52–1.60 | 9.6–11.5 | chamber acid fertilizer acid |
78–80% | 1.70–1.73 | 13.5–14.0 | tower acid Glover acid |
93.2% | 1.83 | 17.4 | 66 °Bé ("66-degree Baumé") acid |
98.3% | 1.84 | 18.4 | concentrated sulfuric acid |
"Chamber acid" and "tower acid" were the two concentrations of sulfuric acid produced by the lead chamber process, chamber acid being the acid produced in the lead chamber itself (<70% to avoid contamination with nitrosylsulfuric acid) and tower acid being the acid recovered from the bottom of the Glover tower. [12] [13] They are now obsolete as commercial concentrations of sulfuric acid, although they may be prepared in the laboratory from concentrated sulfuric acid if needed. In particular, "10M" sulfuric acid (the modern equivalent of chamber acid, used in many titrations), is prepared by slowly adding 98% sulfuric acid to an equal volume of water, with good stirring: the temperature of the mixture can rise to 80 °C (176 °F) or higher. [13]
Sulfuric acid reacts with its anhydride, SO
3 , to form H
2 S
2 O
7 , called pyrosulfuric acid, fuming sulfuric acid, Disulfuric acid or oleum or, less commonly, Nordhausen acid. Concentrations of oleum are either expressed in terms of % SO
3 (called % oleum) or as % H
2 SO
4 (the amount made if H
2 O were added) common concentrations are 40% oleum (109% H
2 SO
4 ) and 65% oleum (114.6% H
2 SO
4 ). Pure H
2 S
2 O
7 is a solid with melting point of 36 °C.
Pure sulfuric acid has a vapor pressure of <0.001 mmHg at 25 °C and 1 mmHg at 145.8 °C, [14] and 98% sulfuric acid has a <1 mmHg vapor pressure at 40 °C. [15]
Pure sulfuric acid is a viscous clear liquid, like oil, and this explains the old name of the acid ('oil of vitriol').
Commercial sulfuric acid is sold in several different purity grades. Technical grade H
2 SO
4 is impure and often colored, but is suitable for making fertilizer. Pure grades, such as USP grade, are used for making pharmaceuticals and dyestuffs. Analytical grades are also available.
Nine hydrates are known, but four of them were confirmed to be tetrahydrate (H2SO4·4H2O), hemihexahydrate (H2SO4· 6 + 1 ⁄ 2 H2O) and octahydrate (H2SO4·8H2O).
Polarity and conductivity Edit
Species | mMol/kg |
---|---|
HSO − 4 | 15.0 |
H 3 SO + 4 | 11.3 |
H 3 O + | 8.0 |
HS 2 O − 7 | 4.4 |
H 2 S 2 O 7 | 3.6 |
H 2 O | 0.1 |
Anhydrous H
2 SO
4 is a very polar liquid, having a dielectric constant of around 100. It has a high electrical conductivity, caused by dissociation through protonating itself, a process known as autoprotolysis. [16]
The equilibrium constant for the autoprotolysis is [16]
The comparable equilibrium constant for water, Kw is 10 −14 , a factor of 10 10 (10 billion) smaller.
In spite of the viscosity of the acid, the effective conductivities of the H
3 SO +
4 and HSO −
4 ions are high due to an intramolecular proton-switch mechanism (analogous to the Grotthuss mechanism in water), making sulfuric acid a good conductor of electricity. It is also an excellent solvent for many reactions.
Reaction with water and dehydrating property Edit
Because the hydration reaction of sulfuric acid is highly exothermic, dilution should always be performed by adding the acid to the water rather than the water to the acid. [17] Because the reaction is in an equilibrium that favors the rapid protonation of water, addition of acid to the water ensures that the acid is the limiting reagent. This reaction is best thought of as the formation of hydronium ions:
Because the hydration of sulfuric acid is thermodynamically favorable and the affinity of it for water is sufficiently strong, sulfuric acid is an excellent dehydrating agent. Concentrated sulfuric acid has a very powerful dehydrating property, removing water (H2O) from other chemical compounds including sugar and other carbohydrates and producing carbon, heat, and steam.
In the laboratory, this is often demonstrated by mixing table sugar (sucrose) into sulfuric acid. The sugar changes from white to dark brown and then to black as carbon is formed. A rigid column of black, porous carbon will emerge as well. The carbon will smell strongly of caramel due to the heat generated. [19]
C 12 H 22 O 11 ⏞ sucrose → H 2 SO 4 12 C (black graphitic foam) + 11 H 2 O (g,l) If you spill some sulfuric acid on your skin, you want to wash it off with copious amounts of running, cold water as soon as possible. Water is less dense than sulfuric acid, so if you pour water on the acid, the reaction occurs on top of the liquid. If you add the acid to the water, it sinks. Any wild and crazy reactions have to get through the water or beaker to get to you. How do you remember this? Here are some mnemonics: Personally, I don't find any of those mnemonics easy to remember. I get it right because I figure if I get it wrong, I'd rather have a whole container of water splash on me than a whole container of sulfuric acid, so I take my chances with the small volume of acid and the large volume of water. Saline soils represent a group of soils in which percentages of soluble salts, usually chlorides and sulphates of the alkali bases are very high. The pH of saline soils are always high. In India saline soils occur in many provinces, as U.P., West Bengal, Punjab, Bihar, Orissa, Maharashtra Tamil Nadu, M.P., Andhra Pradesh, Gujarat, Delhi and Rajasthan covering an area of about 7 million hectares. There are 4 major tracts in India where salinity problem is acute. (a) The arid tract of Rajasthan and Gujarat, (b) Semi-arid alluvial tracts of Punjab, Haryana and Uttar Pradesh, (c) The arid and semi-arid tracts of Southern States, and In U.P, the saline (usar) soils are distributed in Kanpur, Lucknow, Hardoi, Unnao, Allahabad, Rai Bareh, Azamgarh and many other districts covering about 1.29 million hectares. In Punjab alone saline soil covers about 2 million hectare area. In U.P. and Punjab the saline soils are gradually increasing in area. These lands are known by a variety of names in local agricultural parlance. By far the most common of them is mar derived from the Sanskrit word Ushtra meaning sterile or barren. Other terms like reh, char, lone, thur or shora are also popular. The word alkali is of Arabic origin meaning ash-like and is used to designate hard and intractable soils generally known by the names rakkar, kallar, bara and bari. The salty soils are of three types: (i) Saline or solonchak or white alkali soils: In these, salinity is caused by soluble salts other than alkali salts. They have high soluble salts and low exchangeable sodium. (ii) Alkali or sodic or solonetz or black alkali soils: These are formed by accumulation of alkalies, such as Na, K etc. in excess. Such soils have low salt content but high exchangeable sodium. (iii) Saline-alkali soils: In these, alkali and other soluble salts have combined effects. They are also called saline sodic as they have high salt content and high exchangeable sodium. The United States Salinity Laboratory recently designated these soils scientifically on the basis of soil analysis following the ideas of Sigmond and Gedroiz (1954) (Table 23.4). Three classes of salty soil: Soils in which salinity is mainly due to accumulation of alkali salts are called alkali soils or usar soils. High alkalinity in the soil adversely affects the plant growth, thereby reduces the crop yield. Such sterile or unproductive soils are called barren soils. The main salts present in the alkali soils are Na2SO4, K2SO4, NaCl, and KCl. Types of alkali soils: These soils are of two types: (i) Black alkali soils—In these soils, Na2CO3 is found in excess. (ii) White alkali soils—In this group, NaCl is present in excess. Russians call such soils as solonchack. Bertholet suggested that Na2CO3 was formed in black alkali soil by interaction of NaCl and CaCO3. Factors Which Make the Soils Alkaline: 1. Poor drainage in arid region, 2. Rapid evaporation of alkaline soil solution, and 3. Excess uptake of alkaline salts and little percolation. In arid and semi-arid regions, the rainfall is too low to leach or remove the saline matter from the top soils. Besides this, water along with dissolved alkali salts moves upward by capillary action which on reaching to the soil surface evaporates and the salts accumulate in the form of a hard layer or pan in the subsoil. This hard layer is responsible for impermeability of such soils. Miller is of the opinion that many plants absorb excess acidic ions, e.g., NO – 3, than the basic ions. This excessive removal of acidic ions results in the accumulation of basic ions which make the soil alkaline. According to a chemical hypothesis, alkali soils may result in the following steps: (a) Reaction between NaCl or KCl and soil (S): NaCl + S (Soil) → Na (S) + CI – ion (b) Then the soluble products are leached away from the soil surface by drainage water, and (c) Finally, reaction between insoluble Na (S) complex and carbonates. 2 Na (S) + CaCO3 → Ca (S) (alkaline) + Na2CO3 (alkaline) Effects of alkali salts on vegetation: The alkali salts show the following effects on plants: (i) Due to excessive accumulation of salts, concentration of soil solution becomes high. This decreases absorption of nutrients by plants and causes plasmolysis of cell cytoplasm in the plants which may be fatal sometimes. All these effects are responsible for stunted growth of plants. (ii) If sodium is absorbed by the plants in excess, it shows toxic effects. Chloride salt of alkaline elements causes the death of trees. BaCO3 and BaCl are toxic to all plants. (iii) Presence of excess salts in the soil retards the germination of seeds and growth of seedlings. Plants die before bearing fruits. (iv) Alkali salts in the soil also affect the plant growth by reducing the size of leaves in alkali soil, plant roots remain superficial, bark of stem turns brown or black, green tissues are less developed. Alkali tolerance in plant: Some plants are resistant to alkali salts. Barley, wheat oats sorghum, sugar-beet, berseem are best suited to grow in alkaline soil. Cotton and grapes are also alkah tolerants. Uppal et al (1961) prepared a list of crops that can be grown at various stages of reclamation. They can be categorized as high, medium and low salt tolerant crops. High salt tolerant crops are Dhaincha, paddy, sugarcane in kharif and oat, berseem, lucerne, sanji (Trigonella spp), and barley in rabi. Medium salt tolerant crops to be tried during second stage of reclamation are castor, cotton, jowar, bajra, and maize for kharif and mustard and wheat for rabi. Low salt tolerant crops are sesamum, moong, urd, arhar, and sannhemp in kharif and gram peas, linseed during rabi. Uppal et al also listed babul, dhak, jhand, khair, chokra, neem, Lasora, Sisham, siris, bahera and reonjha as trees that can be planted on saline alkali soils. The alkali tolerance of plants depends upon: (i) Physiological constitution of cell cytoplasm of the plant. (ii) Length of roots. Shallow roots are more affected by alkalinity than the deeper roots. (iii) Alkali salts reduce and correct the soil acidity and improve the physical conditions of the soils. (iv) Calcium salts provide calcium to the plants. (v) Many alkali salts change toxic elements, such as aluminum and Mn. into their harmless compounds. Reclamation of Alkali, Saline and Saline-Alkali Soils: The excessive accumulation of alkali salts in the soils is injurious for plants growth It is necessary, therefore, to reduce the percentage of salts to optimum or normal level so that plants may grow luxuriantly in such soils. There are several methods of reclamation which can be grouped as follows: (A) Chemical method in which some chemicals are added to the soil in order to brine the alkalinity to desired level. (B) Mechanical practices such as improving drainage and leaching, mechanical shattering of clay pans, and scrapping. (C) Cultural method (growing salt tolerant plants). Since fundamental causes in various groups of salty soils are different, their reclaiming techniques are different. Hence, these are discussed separately. 1. Reclamation of Alkali Soils: Alkali soils are best reclaimed by the following methods: (A) Chemical method: (1) By cationic exchange (replacement of alkali from soil colloids by calcium ions). Application of calcium sulphate (gypsum) in the soil reduces alkalinity to a great extent and makes the soil fertile. The reaction proceeds in the following way: Good drainage leaches away Na2SO4. (2) Alkali salt percentage can also be reduced in the soil by the use of acid forming chemical amendments such as sulphur, ferrous sulphate and limestone. Sulphur, when applied to the soil, oxidises and forms sulphuric acid which converts carbonates of sodium and potassium to Na2SO4 and K2SO4 respectively that may be removed from top soil by drainage water. The amount of gypsum and sulphur required to reclaim the alkali soils will be different depending upon the degree of alkalinity, drainage and buffering capacity of soils. The types of reaction which occur when an amendment is applied to an alkali soil are given below: In the next step, if soil is calcareous— But if the soil is non-calcareous— (v) 2Na-Clay + H2S04= 2H-clay + Na2S04 (2) With lime-sulphur: Now if the soil is calcareous— (iii) 2Na-Clay + CaSO4 = Ca-Clay + Na2SO4 But if the soil is non-calcareous— (3) With ferrous sulphate: Now if the soil is calcareous— But if the soil is non-calcareous— (4) With limestone on non-calcareous soils: (i) Na-Clay + H2O = H-Clay + NaOH (5) With any H-Clay: The use of pyrite (FeS2) as an amendment is a recent development in the chemical amelioration and reclamation of alkali soils. In presence of moisture and air, pyrite is converted into sulphuric acid which then replaces exchangeable sodium by hydrogen or calcium released from insoluble calcium present in the soil. In addition it is said to correct iron deficiency and lime induced iron chlorosis in alkali soils. It is important to mention that the formation of H2SO4 in the soil by the application of pyrite may take place through chemical and microbiological actions. Pyrite is oxidised according to the following equation suggested by Bloomfield (1973). FeS2 + 2Fe +3 = 3Fe +2 + 2s (Chemical) Sulphur thus formed could be the substrate for thioxidants which convert it into H2SO4. Temple and Kochler (1954) explained the action of ferroxidans on the formation of H2SO4 as follows: FeSO4 formed in the above reaction may be converted into H2SO4 by hydrolysis. In brief, the pyrite is oxidized in soils to ferrous sulphate and sulphuric acid as depicted in the following equation: Both sulphuric acid and ferrous sulphate help in reclamation of calcareous as well as non- calcareous salt affected soils by lowering the pH and solubilising free calcium from calcium carbonate present. The reactions are given below: In salt affected calcareous soils: H2SO4 formed in reaction II reacts as per equations la and lb III. H2SO4 also neutralizes NaHCO3 and Na2CO3 present in these soils. But if the soil is non-calcareous: H2SO4 formed in reaction II acts in similar manner as in reaction I. (3) Dhar’s method. In India, Dr. Neel Ratan Dhar (1935) succeeded in reducing the alkalinity and salinity of the soil by the use of molasses and press-mud. For one acre land he recommended the mixture of the following substances: (i) 2 tons of molasses, (ii) 1-2 tons of press-mud (a waste product of sugar industry) and (iii) 50-100 pounds of P2O5 in the form of basic slag. The molasses is fermented by soil microbes and as a result of fermentation organic acids are produced which lower the alkalinity and increase the availability of phosphates. The press- mud contains Ca which forms calcium salts that reduce the content of exchangeable sodium. Phosphate helps in the microbial fixation of nitrogen into nitrogenous compounds in the soil. (B) Mechanical methods: The alkali salts are removed by: (1) Scraper or by rapidly moving streams of water, (2) Deep ploughing of the land which reduces the alkalinity and makes the soil more permeable. (3) Application of green manures of Dhaincha, guar, jantar (Sesbania aculeata) has been found most successful in reclamation of alkali and saline soils. (4) Spreading of straw and dried grasses and leaves on the alkaline soil. (C) Cultural method: Growing of alkali tolerant crops and plants, such as sugar-beet, rice, patsann (Hibiscus cannabinus), wild indigo and babul in such soils successfully reduces alkalinity. Rice is commonly the first crop grown on salty lands to be reclaimed. In Punjab the usual practice of reclamation of salty lands involves growing of paddy after first initial leaching followed by berseem or senji which has higher water requirement than Dhaincha as green manure which IS followed by sugarcane and then wheat or cotton. Introduction of leguminous crops helps in building up of nitrogen supply and opens the soils. Dhaincha-paddy-berseem rotation has been found to be the best cropping pattern on mild type of alkali soils in Punjab region. In U.P. also, paddy or dhaincha-paddy are the usual crops taken during first stage of reclamation of salty soils. This is followed by berseem or barley in winter. Pulse crops like gram or peas show poor performance. II. Reclamation of saline soil: Saline soil can be reclaimed by the following methods: (1) By lowering the water table 5-6 feet below the surface. In sloppy area, it can be done by making network of 5-6 feet deep trenches at right angles to the slopes. In course of 2 or 3 Successive leaching, harmful salts are removed. A deep ploughing is also helpful in reclamation of saline soil. This also makes the soil loose and thus facilitates the downward movement of salty water in the soil. (2) Salt tolerant crops, e.g., rice, sugar cane, barley and castor gradually remove salts from the soil. (3) In case of saline soils which do not contain calcium salts, the addition of CaSO4 (gypsum) is beneficial. Supply of calcium in the soil can indirectly be maintained by of organic matters which on decomposition produce CO2. The CO2 gas, so produced, combines with insoluble calcium carbonate in moist condition to form soluble calcium bicarbonate. This also reduces alkalinity. (4) Application of green manure, organic manures, organic residues, acids or acid formers is yet another good way to reduce salinity. III. Reclamation of saline-alkaline soil: Here the problem of reclamation is two-fold because of: (a) Heavy accumulation of different types of salts, (b) Poor percolation due to the presence of hard clay pan and highly dispersed sodium clay. Such soil can be reclaimed by: (i) Mechanical shattering of clay pans. This helps in downward movement of water. (ii) Application of gypsum in the soil. This is followed by flushing with plenty of water. (iii) Green maturing with Dhaincha (Sesbenia aculeata). (iv) Growing of salt tolerant plants, e.g., paddy in kharif and oat and barley in rabi seasons are recommended for such soils. , Schoonover (1959) worked on the soils of India and enlisted the following technical requirements for reclamation of saline and alkaline soils: (1) Necessity of good drainage. (2) Availability of sufficient water to wash the excess salts from the top soils. (3) Good soil management including land leveling, good bonding for irrigation and recent and advanced agronomic practices.
Alkali Soils: Factors, Effects and Reclamation