Chemistry
Gas Solubility
Gas solubility refers to the ability of a gas to dissolve in a liquid. It is influenced by factors such as temperature, pressure, and the nature of the gas and liquid. Henry's law describes the relationship between the pressure of the gas and its solubility in the liquid, with higher pressures leading to greater solubility.
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10 Key excerpts on "Gas Solubility"
eBook - PDF- David Pye, Innocent Joseph, Angelo Montenero(Authors)
- 2005(Publication Date)
- CRC Press(Publisher)
These released gases interact with the gases in the furnace atmosphere and in the glass melt, and dissolve into the melt. The solubility of gases in glass melts, as that in normal liquids, is defined as the equilibrium concentration of dissolved gases in those liquids or melts at a given gas pressure and given temperature. The solubility of gases in glass melts depends on temperature, glass composition and on gas fugacities (function of gas partial pressures). These factors, as well as the transport of dissolved gases by diffusion, are of great impor-tance to gas release and gas absorption mechanisms in melting, refining and condi-tioning. The formation, change of content, growth, shrinkage and general behavior of gas bubbles in glass can essentially be understood by understanding solubility and diffusivity of gases in melts. Additionally, the amount and type of dissolved gases in glasses can influence the properties of these glasses. For instance, the influence of dissolved gases on density, viscosity, thermal expansion, surface tension, refractive index and electric resistance has been proven [1–6]. The solution of gases in molten silicates or borates and in aqueous solutions seems to be the result of the development of two types of processes: one of a physical nature, the other of a chemical nature. In chemical solubility, chemical reactions occur during the process of dissolu-tion, and the interaction between gas and melt is strong when a solution of water vapor, hydrogen, sulfur dioxide, carbon dioxide, oxygen in the presence of multi-valent ions, and nitrogen at reducing conditions is present in the melt. In the case of physical solubility, the interaction forces between gases and melts are considerably weaker due to the Van der Waals forces with a solution of inert gases or nitrogen at oxidizing conditions. The amount of physically dissolved gases at normal pressure is only 1/1000 to 1/10000 of the quantity that can be dissolved chemically.
eBook - PDF- James Cameron(Author)
- 2012(Publication Date)
- Academic Press(Publisher)
This point cannot be over-emphasized: equilibrium occurs at equal partial pressures, not necessarily equal concentrations. It is furthermore a common kind of problem, for example in assessing exchange between water and blood or blood and cerebrospinal fluid. 2.5. DIFFUSION 19 1 2 τ 1 0 -10 I 20 Temp., C 3 0 —i 40 10 20 30 Salinity, ppt Fig. 2.3 The solubility of oxygen as a function of temperature in pure water (left) and as a function of salinity at 10°C (right). The units of solubility are ml 0 2 L 1 equilibrated with a water-saturated atmosphere of 20.94% oxygen. The solubility of gases is influenced by many factors, only one of which, the nature of the solvent, has been mentioned. Temperature and the solubility coefficient are inversely but not linearly related (Fig. 2.3). Increasing ionic strength reduces Gas Solubility, but again, not linearly. The solubility of gases is for practical purposes insensitive to the presence of other gases and insensitive to the nature of the electrolytes present. The solubilities of some common gases in water are given in Table 2.2, and some more detailed tables of Gas Solubility have been provided in Appendix 2. In the above discussion, only the physical solubility of the molecule in question has been discussed; chemical reactions that bind solute gas molecules to the solvent, and thereby increase its concentration, are not germane to the discussion of solubility, although such binding reactions are of great importance physiologically, as detailed in subsequent chapters. —i 40 2.5. DIFFUSION The mechanics of diffusion of gases can be imagined by likening the process to what would happen in a closed room with several thousand small elastic balls in violent motion on one side of the room.
eBook - PDF- Allan Blackman, Steven E. Bottle, Siegbert Schmid, Mauro Mocerino, Uta Wille(Authors)
- 2022(Publication Date)
- Wiley(Publisher)
However, not all gases become less soluble as the temperature increases; for example, the solubilities of H 2 , N 2 , CO, He and Ne in common organic solvents, such as toluene and acetone, actually increase with increasing temperature. You can see from these examples that predicting solubilities even in simple systems is fraught with difficulty. CHAPTER 10 Solutions and solubility 459 The solubility of a gas in a liquid is affected not only by temperature but also by pressure. For example, the gases in air, chiefly nitrogen and oxygen, while not very soluble in water under ordinary pressures, become increasingly soluble as their pressures are increased (see figure 10.5). FIGURE 10.5 Gas Solubility in water versus pressure of the undissolved gas for nitrogen and oxygen. The amount of gas that dissolves increases as the pressure of that undissolved gas increases. 1 × 10 5 2 × 10 5 3 × 10 5 4 × 10 5 5 × 10 5 6 × 10 5 Pressure (Pa) g gas 100 g H 2 O at 25 °C Solubility O 2 N 2 0.025 0.020 0.015 0.010 0.005 We can rationalise this observation by again considering the below equilibrium and looking at the effect of increasing the pressure of the undissolved gas on the position of this equilibrium. gas undissolved ⇌ gas dissolved FIGURE 10.6 Bottled carbonated beverages fizz when the bottle is opened because the sudden drop in pressure causes a sudden drop in Gas Solubility. The reaction quotient expression for this equi- librium can be written in a form that involves both the pressure of the undissolved gas and the concentration of the dissolved gas. Q = [gas dissolved ] ( p(gas undissolved ) p o ) We can see from this that Q is inversely pro- portional to p(gas undissolved ). Thus, if we increase the pressure of the undissolved gas at constant temperature, we decrease Q so that Q < K. To restore equilibrium and make Q = K, the equi- librium position shifts towards the right-hand side to increase Q by increasing [ gas dissolved ] .
eBook - ePubEnvironmental Engineering
Principles and Practice
- Richard O. Mines, Jr.(Authors)
- 2014(Publication Date)
- Wiley-Blackwell(Publisher)
The carbonate system is the most important natural buffering system encountered in environmental engineering. It is directly related to alkalinity, which is defined as the buffering capacity of a water to resist a change in pH when an acid is added.- Alkalinity is measured by titrating a sample of water with to a pH of approximately 4.5.
- Mathematically, alkalinity is defined by the following equation:
Liquid-solid species that are partially soluble or insoluble can be explained using the solubility product The solubility of most substances increases with temperature; however, there are exceptions:- Salts with low values generally have low solubilities.
- It is impossible to predict the solubilities of various compounds solely based on values since solids that dissolve into two or three ions will generally have higher solubilities.
Proper application of gas phase laws is essential for designing gas transfer systems, gas strippers, determining saturation concentration of dissolved gases in aqueous solutions, and understanding the relationship between pressure and volume of a gas and between temperature and volume of a gas.- The ideal gas law is used to solve for pressure, volume, moles, or temperature, given three of these four parameters.
- Dalton's law of partial pressure states that the total pressure exerted by a mixture of gases is the sum of the partial pressures of each gas present.
- Raoult's law relates the partial pressure of the gaseous component present above a liquid to the vapor pressure of the pure component and the mole fraction of the pure component in the liquid phase.
- Henry's law is used for calculating the solubility of a gas in a liquid, or to describe the equilibrium condition between the gas and liquid phases.
- There are several forms of Henry's law, so special attention should be placed on the dimensions on the Henry's law constant in order to apply the appropriate equation expressing Henry's law.
Organic chemistry is the study of carbon-containing compounds and their properties. Organic compounds are important because: they form the basis of all life; they are used in the production of pesticides, herbicides, insecticides, polymers, antibiotics, hormones, and alcohols; and they cause detrimental affects to the environment, since many of them are toxic and/or carcinogenic.
eBook - ePub- Saul Goldman, Manuel Solano-Altamirano, Kenneth Ledez(Authors)
- 2017(Publication Date)
- Academic Press(Publisher)
2Driving force of gas-bubble growth and dissolution
Abstract
Solubility, saturation, supersaturation, and undersaturation are all explained in the context of gas-liquid solutions. Solutions composed both of one and several different gaseous solutes are considered. The chemical potential of a specific chemical species is introduced and its basic role in solute distribution is described. Solute distribution or redistribution occurs so as to lower the value of its chemical potential, because doing so lowers the system free energy. This is made manifest within a single phase by solutes tending to spontaneously diffuse down their concentration gradients, from higher to lower concentrations. For a pair of contiguous phases, such as a gas and a liquid, the tendency to lower the system free energy causes the volatile solute to be driven from the phase in which its chemical potential is larger to the phase in which it is lower. The crucial role of surface tension on gas bubble pressure is described. It is particularly important for small gas bubbles (<50 μ), and it is expressed quantitatively by the Young-Laplace equation. Surface tension tends to increase the pressure acting on the contents of a gas bubble beyond what it would be from the effect of ambient hydrostatic pressure only.Keywords
Chemical potential; Gas Solubility; Surface tension; Supersaturation; Undersaturationδ (ε − Tη + pV ) = 0The condition of stable equilibrium is that the value of the expression in the parenthesis shall be a minimum. J.W. GibbsMain Topics• Solubility• Solute flow• Ideal gas law• Surface tension• Saturation• Supersaturation• UndersaturationMedical Matters• The medical/physical dichotomy2.1 Introduction
Most of this book is about the dynamics of gas-bubble growth and dissolution in the body, and its practical implications for diving and clinical practice. Our orientation is more physical than is typical, and this includes a greater than usual emphasis on providing the physical basis of the underlying phenomena, at a state-of-the-art level. This, in turn, requires some separation of the “basic stuff,” from much of the medical and physiological complexity that accompanies these phenomena. Therefore, in order to set out the physical principles as cleanly and clearly as we can we will, in the chapters that deal largely with physical principles (Chapters 2 –6 and 8
eBook - PDF- Trevor M Letcher(Author)
- 2007(Publication Date)
- Royal Society of Chemistry(Publisher)
23 49 Solubility of Gases The solubility of a gas in water (at given temperature and pressure) is strongly affected by the presence of a strong electrolyte. Adding a strong electrolyte usually results in a decrease of the Gas Solubility (‘‘salting-out effect’’). For example, Figure 6 shows experimental and correlation results for the solubility of carbon dioxide (a sparsely soluble gas) in water as well as in aqueous solutions of the single salts sodium nitrate and ammonium nitrate at T E 313 K. 10 Carbon dioxide is ‘‘salted out’’ by sodium nitrate, and it is ‘‘salted in’’ by ammonium nitrate. For example, for a solution containing about 0.5 mol kg 1 CO 2 and 10 mol kg 1 NaNO 3 (NH 4 NO 3 ), the total pressure is about 7 MPa (1.9 MPa), whereas it is about 2.4 MPa above the salt-free solution. The solubility of the strong electrolyte in water might also be affected by the presence of a gas, in particular, if that gas is reasonably soluble in water. For example, at T E 353 K, B 3 mol of Na 2 SO 4 dissolve in 1 kg of pure liquid water, whereas only B 2 ( B 1) mol of that salt dissolve in a solution consisting of 1 kg of pure water and B 3.5 ( B 7.7) mol of ammonia. 4 All of those effects have been successfully described by applying the well-known vapor–liquid and solid–liquid equilibrium conditions, and by describing the properties of the liquid and the gaseous phases by means of Pitzer’s molality-scale-based Gibbs excess energy model 48,49 and the virial equation of state, respectively. That Pitzer’s model is based on the unsymmetric con-vention and is therefore particularly suited for describing the influence of strong electrolytes on the solubility of gases in liquid water, when the amounts of the solute components (gas and strong electrolytes) is remarkably smaller than the amounts of the solvent (water).
eBook - PDFHandbook of Property Estimation Methods for Chemicals
Environmental Health Sciences
- Donald Mackay, Robert S. Boethling, Donald Mackay, Robert S. Boethling(Authors)
- 2000(Publication Date)
- CRC Press(Publisher)
They tend to have larger air-water partition coefficients or Henry’s law 126 Handbook of Property Estimation Methods for Chemicals constants, and they tend to partition more into solid and biotic phases such as soils, sedi-ments, and fish. As a result, it is common to correlate partition coefficients from water to these media with solubility in water, as other chapters discuss. 7.2 Theoretical Foundation Solubility normally is measured by bringing an excess amount of a pure chemical phase into contact with water at a specified temperature, so that equilibrium is achieved and the aqueous phase concentration reaches a maximum value. It follows that the fugacities or partial pressures exerted by the chemical in these phases are equal. Assuming that the pure chemical phase properties are unaffected by water, the pure phase will exert its vapor pres-sure P S (Pa) corresponding to the prevailing temperature. The superscript S denotes satu-ration. In the aqueous phase, the fugacity can be expressed using Raoult’s Law with an activity coefficient γ : (1) where x is the mole fraction of the chemical in aqueous solution, and is the vapor pres-sure of pure liquid phase chemical, again at the specified temperature. 7.2.1 Equilibrium Situations Four possible equilibrium situations may exist, depending on the nature of the chemical phase, each of which requires separate theoretical treatment and leads to different equations for expressing solubility. These equations form the basis of the correlations discussed later. 7.2.1.1 Pure Chemical is an Immiscible Liquid (e.g., Benzene) In this case, P S is also . Thus the product x γ is 1.0 and x is 1/ γ . Sparingly soluble sub-stances are such because the value of γ is large. For example, at 25°C benzene has a solubility in water of 1780 g/m 3 or 22.8 mol/m 3 . Since 1m 3 of solution contains approximately 10 6 /18 mol water (1m 3 is 10 6 g and 18 g/mol is the molecular mass of water), the mole fraction x is 22.8/(10 6 /18) or 0.00041.
eBook - PDFGeneral, Organic, and Biological Chemistry
An Integrated Approach
- Kenneth W. Raymond(Author)
- 2012(Publication Date)
- Wiley(Publisher)
total pressure of mixture of gases is the sum of the individual (partial) pressures of each gas (P total = P A + P B + P C + ….). 4. Define the terms pure A pure substance consists of just one element or 6.4 6.8 6.51–6.58 substance, homogeneous compound. Mixtures of pure substances can be mixture, and heterogeneous homogeneous (uniformly distributed) or heterogeneous mixture. For a homogeneous (not uniformly distributed). In a homogeneous mixture mixture, explain what (solution), the solvent is present in the greatest amount differentiates solutes from and solutes in lesser amounts. a solvent. 5. Describe the effect that As temperature is increased, the solubility of gases in 6.4 6.59–6.64 temperature has on the water decreases. For most liquids and solids, a rise in solubility of gases, liquids, temperature leads to an increased solubility in water. and solids in water. 6. Use solubility rules to predict Depending on the water solubility of the products, some 6.5 6.9, 6.10 6.65–6.76 whether or not a reaction reactions of aqueous ionic compounds can lead to the between ionic compounds formation of precipitates. From the balanced equation will produce a precipitate. for a precipitation reaction, an ionic equation can be For a precipitation reaction, written (soluble reactants and products are listed as write the ionic and net individual ions). Removing spectator ions (appear the ionic equation. same on both sides of the reaction arrow) converts an ionic equation into a net ionic equation. 7. Explain Henry’s law. The solubility of a gas in a liquid is proportional to the 6.6 6.11 6.77–6.80 pressure of the gas over the liquid (the higher the pressure, the greater the solubility of the gas).
- Jan Rydberg(Author)
- 2004(Publication Date)
- CRC Press(Publisher)
In this condition each particle of the solute (molecule or ion) is very remote from any neighbor and has no environment with which to interact. If B is polyatomic, it does have its internal degrees of freedom, such as bond vibrations and rotation of the particle. If this ideal gaseous particle B is introduced into a liquid A at a given temperature and pressure, all of the solute-solvent interactions become “switched on,” the solvation process takes place, and the Gibbs energy of solvation, ∆ solv G B , is released. In many cases the process of dissolution of a gaseous solute in a liquid solvent can, indeed, be carried out experimentally—for instance, when propane or carbon dioxide is dissolved in water to give a solution at a given gas pressure. The Gibbs energy change for the process of dissolution of the gaseous solute B, ∆ soln G B , is the driving force for the material transfer. When equilibrium is reached, ∆ soln G B becomes zero (since, at equilibrium, no more net transfer occurs). The following equation then holds: where is the standard molar Gibbs energy of solvation of the solute B, defined by Eq. (2.9) and c B is its molar concentration (moles per unit volume) in the designated phases, (1) for liquid and (g) for gaseous. Equilibrium is generally assumed for the processes discussed elsewhere in this chapter, and is only emphasized here for Eq. (2.9) by the subscript eq for ∆ soln G B and the ratio of concentrations, c B (1)/c B (g). The concentration in the gas phase is, of course, given by the pressure according to the ideal gas law c B (g)=n B /V=P/RT. The ratio of the concentrations is known as the Bunsen coefficient, K B(B,A) , for the solubility of the gaseous solute B in liquid A. At low pressures and concentrations K B(B,A) depends only on the temperature and is independent (2.9) Solvent extraction principles and practice 38
- G. T. Hefter, R. P. T. Tomkins, G. T. Hefter, R. P. T. Tomkins(Authors)
- 2003(Publication Date)
- Wiley(Publisher)
Various factors affect the accur- acy of the methods for the determination of solubility. However, the sensitiv- ity of these methods to such factors as history effects (annealing, pretreatment by exposing to high pressure gas), the influence of the protocol of the sample preparation or the presence of the residual solvent, etc., make the task of achieving higher accuracy quite difficult. 7 REFERENCES 1. C.S. Venable and T. Fuwa. The solubility of gases in rubber and rubber stock and effect of solubility on penetrability, J. Ind. Eng. Chem. (1922) 14, 13942. 2. P. Meares. Solubility of gases in polyvinyl acetate, T rans. Faraday Soc. (1958) 54, 4046. 3. A.S. Michaels and R.B. Parker. The determination of solubility constants for gases in polymers, J. Phys. Chem. (1958) 62, 160405. 4. H. Odani, K. Taira, T. Yamaguchi, N. Nemoto and M. Kurata. Solubilities of inert gases in styrenebutadienestyrene copolymers, Bull. Inst. Chem. R es. Kyoto Univ. (1975) 53, 40923. 5. J.L. Lundberg, M.B. Wilk and M.J. Huyett. Estimation of diffusivities and solubi- lities from sorption studies, J. Polym. S ci. (1962) 57, 27599. 6. J.L. Lundberg, M.B. Wilk and M.J. Huyett. Sorption studies using automation and computation, Ind. Eng. Chem. Fundam. (1963) 2, 3743. 7. W.R. Vieth, P.M. Tam and A.S. Michaels. Dual sorption mechanism in glassy polystyrene, J. Coll. Interface S ci. (1966) 22, 36070. 8. S.A. Stern and A.H. DeMeringo. Solubility of carbon dioxide in cellulose acetate at elevated pressures, J. Polym. Sci.: Polym. Phys. Ed. (1978) 16, 73451. 9. V.M. Shah, B.J. Hardy and S.A. Stern. Solubility of carbon dioxide, methane, and propane in silicon polymers: Effect of polymer side chains, J. Polym. Sci.: Part B: Polym. Phys. (1986) 24, 203347 10. H.B. Hopfenberg (Ed). Permeability of Plastic Films and Coatings to Gases, V apors. and L iquids, Plenum Press, New York (1974) pp. 285299.
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