Carbon dioxide buffering

After interesterification has proceeded to the desired point, the catalyst is destroyed by adding water and carbon dioxide. Carbon dioxide buffers the caustic to a lower pH and minimizes saponification of the lard. The neutralized lard is heated to melt the trisaturated glyceride crystals. Soaps are removed by conventional water washing and centrifuging, and the lard is dried in a continuous-vacuum drier. A basic flow chart for the process is shown in Fig. 12-8. 

Figure 8 Electron capture Cl mass spectra of tetracyanoethylene and tetracyanoquinodimethane using CH4 and CO2 as buffer gases. Reprinted with permission from Sears LJ and Grimsrud EP (1989) Eiimination of unexpected ions in electron capture mass spectrometry using carbon dioxide buffer gas. Analytical Chemistry, 61 2523-2528. Copyright (1989) American Chemical Society.

Alkaline solutions of mononitroparaffins undergo many different reactions when stored for long periods, acidified, or heated. Acidification of solutions of mononitro salts is best effected slowly at 0°C or lower with weak acids or buffered acidic mixtures, such as acetic acid—urea, carbon dioxide, or hydroxyl ammonium chloride. If mineral acids are used under mild conditions, eg, dilute HCl at 0°C, decomposition yields a carbonyl compound and nitrous oxide (Nef reaction). 

An additional mole of ammonium sulfate per mole of final lactam is generated duting the manufacture of hydroxylamine sulfate [10039-54-0] via the Raschig process, which converts ammonia, air, water, carbon dioxide, and sulfur dioxide to the hydroxylamine salt. Thus, a minimum of two moles of ammonium sulfate is produced per mole of lactam, but commercial processes can approach twice that amount. The DSM/Stamicarbon HPO process, which uses hydroxylamine phosphate [19098-16-9] ia a recycled phosphate buffer, can reduce the amount to less than two moles per mole of lactam. Ammonium sulfate is sold as a fertilizer. However, because H2SO4 is released and acidifies the soil as the salt decomposes, it is alow grade fertilizer, and contributes only marginally to the economics of the process (145,146) (see Caprolactam). 

Potassium Permanganate. Probably the most widely used process for removing traces of hydrogen sulfide from carbon dioxide is to scmb the gas with an aqueous solution saturated with potassium permanganate [7722-64-7]. Sodium carbonate is added to the solution as buffer. The reaction is as foUows ... 

Cosmetics and Toiletries. Citric acid and bicarbonate are used in effervescent type denture cleansers to provide agitation by reacting to form carbon dioxide gas. Citric acid is added to cosmetic formulations to adjust the pH, act as a buffer, and chelate metal ions preventing formulation discoloration and decomposition (213—218). 

Ion-selective electrodes can also become sensors (qv) for gases such as carbon dioxide (qv), ammonia (qv), and hydrogen sulfide by isolating the gas in buffered solutions protected from the sample atmosphere by gas-permeable membranes. Typically, pH glass electrodes are used, but electrodes selective to carbonate or sulfide may be more selective. 

Manufacturers added exhaust gas recirculation (EGR) systems to counter the increased in-cylinder NO. formation associated with higher operating temperatures. The EGR recycles a portion of the exhaust stream back into the engine intake air. The relatively inert exhaust gas, containing carbon dioxide and water but little oxygen, serves as a combustion buffer, reducing peak combustion temperatures. 

Notes. (1) Somewhat sharper end points may be obtained if the sample of water is first acidified with dilute hydrochloric acid, boiled for about a minute to drive off carbon dioxide, cooled, neutralised with sodium hydroxide solution, buffer and indicator solution added, and then titrated with EDTA as above. 

Details for the preparation of the solutions referred to in the table are as follows (note that concentrations are expressed in molalities) all reagents must be of the highest purity. Freshly distilled water protected from carbon dioxide during cooling, having a pH of 6.7-7.3, should be used, and is essential for basic standards. De-ionised water is also suitable. Standard buffer solutions may be stored in well-closed Pyrex or polythene bottles. If the formation of mould or sediment is visible the solution must be discarded. 

R FS. 0.05m Potassium hydrogenphthalate. Dissolve 10.21 g of the solid (dried below 130 °C) in water and dilute to 1 kg. The pH is not affected by atmospheric carbon dioxide the buffer capacity is rather low. The solution should be replaced after 5-6 weeks, or earlier if mould-growth is apparent. 

P2. 0.025m Phosphate buffer. Dissolve 3.40g of KH2P04 and 3.55 g of Na2HP04 (dried for 2 hours at 110-113 °C) in carbon-dioxide-free water and dilute to 1 kg. The solution is stable when protected from undue exposure to the atmosphere. 

Erythorbates are safe products and there are no harmful breakdown products, although when early formulations utilized ammonia as a PH buffer (and neutralizer for part of the carbon dioxide), copper corrosion problems resulted. However, erythorbates are not steam-volatile,and consequently there is no post-boiler oxygen scavenging potential available. Thus, in the event of complete breakdown of the product at high pressure, oxygen-induced, ammonia corrosion of copper may continue unchecked. 

Sodium bicarbonate is used as a leavening in breads, as a stomach antacid, as a buffering agent to adjust the acidity or alkalinity of a product, as a mild abrasive in toothpaste, and as an odor absorber. Sodium bicarbonate reacts with acids to release carbon dioxide gas. 

DI water is not equivalent to distilled water in all ways. While the content of most ionic species is very low, it does contain dissolved gases, such as air and carbon dioxide. The latter caused problems in one laboratory when DI water was used for diluting poorly buffered samples for pH measurements. Erratic results were also reported in another case when DI water was used in connection with the determination of trace amounts of boron. The manufacturer explained that when close to exhaustion, the resin used would no longer be effective in holding back traces of this element. 

Figure 6-9. The Bohr effect. Carbon dioxide generated in peripheral tissues combines with water to form carbonic acid, which dissociates into protons and bicarbonate ions. Deoxyhemoglobin acts as a buffer by binding protons and delivering them to the lungs. In the lungs, the uptake of oxygen by hemoglobin releases protons that combine with bicarbonate ion, forming carbonic acid, which when dehydrated by carbonic anhydrase becomes carbon dioxide, which then is exhaled.

The microalgae are cultured in bioreactors under solar or artiflcial light in the presence of carbon dioxide and salts. The bioreactors may be closed systems made of polyethylene sleeves rather than open pools. Optimal conditions for pigment production are low to medium light intensity and medium temperatures (20 to 30°C). Pigment extraction is achieved by cell breakage, extraction into water or buffered solution, and centrifugation to separate out the filtrate. The filtrate may then be partly purified and sterilized by microfiltration and spray dried or lyophilized. 

In the human body, carbon dioxide provides the buffer. This is called the carbonic acid-hydrogen carbonate ion buffer system. This buffer system maintains the body s blood pH within acceptable levels. The main threat to the bloods pH is excess hydrogen ions produced by various chemical reactions in the body. When hydrogen ions are produced, hydrogen carbonate ions in the blood pick them up and convert them to carbonic acid ... 

When calcium carbonate goes into solution, it releases basic carbonate ions (COf ), which react with hydrogen ions to form carbon dioxide (which will normally remain in solution at deep-well-injection pressures) and water. Removal of hydrogen ions raises the pH of the solution. However, aqueous carbon dioxide serves to buffer the solution (i.e., re-forms carbonic acid in reaction with water to add H+ ions to solution). Consequently, the buffering capacity of the solution must be exceeded before complete neutralization will take place. Nitric acid can react with certain alcohols and ketones under increased pressure to increase the pH of the solution, and this reaction was proposed by Goolsby41 to explain the lower-than-expected level of calcium ions in backflowed waste at the Monsanto waste injection facility in Florida. 

Acid-base reactions of buffers act either to add or to remove hydrogen ions to or from the solution so as to maintain a nearly constant equilibrium concentration of H+. For example, carbon dioxide acts as a buffer when it dissolves in water to form carbonic acid, which dissociates to carbonate and bicarbonate ions ... 

A little later, Russell et al.19 tried to obtain methanol from carbon dioxide by electrolysis. Reduction of carbon dioxide to formate ion took place in a neutral electrolyte at a mercury electrode. On the other hand, formic acid was reduced to methanol either in a perchloric acid solution at a lead electrode or in a buffered formic acid solution at a tin electrode. The largest faradaic efficiency for methanol formation from formic acid was ca. 12%, with poor reproducibility, after passing 1900 C in the perchloric acid solution at Pb in a very narrow potential region (-0.9 to -1.0 V versus SCE). In the buffered formic acid solution (0.25 M HCOOH + 0.1 M... 

Halmann reported in 1978 the first example of the reduction of carbon dioxide at a p-GaP electrode in an aqueous solution (0.05 M phosphate buffer, pH 6.8).95 At -1.0 V versus SCE, the initial photocurrent under C02 was 6 mA/ cm2, decreasing to 1 mA/cm2 after 24 h, while the dark current was 0.1 mA/cm2. In contrast to the electrochemical reduction of C02 on metal electrodes, formic acid, which is a main product at metal electrodes, was further reduced to formaldehyde and methanol at an illuminated p-GaP. Analysis of the solution after photoassisted electrolysis for 18 and 90 h showed that the products were 1.2 x 10-2 and 5 x 10 2 M formic acid, 3.2 x 10 4 and 2.8 x 10-4 M formaldehyde, and 1.1 x 10-4 and 8.1xlO 4M methanol, respectively. The maximum optical conversion efficiency calculated from Eq. (23) for production of formaldehyde and methanol (assuming 100% current efficiency) was 5.6 and 3.6%, respectively, where the bias voltage against a carbon anode was -0.8 to -0.9 V and 365-nm monochromatic light was used. In a later publication,4 these values were given as ca. 1% or less, where actual current efficiencies were taken into account [Eq. (24)]. 

An HPLC method was developed that confirmed the photodegradation of [14C] niclosamide in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 1.0°C [70]. These degradates were carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. 

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