Learning ObjectivesBy the end of this section, you will be able to: Show
If you have ever been in a room when a piping hot pizza was delivered, you have been made aware of the fact that gaseous molecules can quickly spread throughout a room, as evidenced by the pleasant aroma that soon reaches your nose. Although gaseous molecules travel at tremendous speeds (hundreds of meters per second), they collide with other gaseous molecules and travel in many different directions before reaching the desired target. At room temperature, a gaseous molecule will experience billions of collisions per second. The mean free path is the average distance a molecule travels between collisions. The mean free path increases with decreasing pressure; in general, the mean free path for a gaseous molecule will be hundreds of times the diameter of the molecule In general, we know that when a sample of gas is introduced to one part of a closed container, its molecules very quickly disperse throughout the container; this process by which molecules disperse in space in response to differences in concentration is called diffusion (shown in Figure 1). The gaseous atoms or molecules are, of course, unaware of any concentration gradient, they simply move randomly—regions of higher concentration have more particles than regions of lower concentrations, and so a net movement of species from high to low concentration areas takes place. In a closed environment, diffusion will ultimately result in equal concentrations of gas throughout, as depicted in Figure 1. The gaseous atoms and molecules continue to move, but since their concentrations are the same in both bulbs, the rates of transfer between the bulbs are equal (no net transfer of molecules occurs). Figure 1. (a) Two gases, H2 and O2, are initially separated. (b) When the stopcock is opened, they mix together. The lighter gas, H2, passes through the opening faster than O2, so just after the stopcock is opened, more H2 molecules move to the O2 side than O2 molecules move to the H2 side. (c) After a short time, both the slower-moving O2 molecules and the faster-moving H2 molecules have distributed themselves evenly on both sides of the vessel. We are often interested in the rate of diffusion, the amount of gas passing through some area per unit time: The diffusion rate depends on several factors: the concentration gradient (the increase or decrease in concentration from one point to another); the amount of surface area available for diffusion; and the distance the gas particles must travel. Note also that the time required for diffusion to occur is inversely proportional to the rate of diffusion, as shown in the rate of diffusion equation. A process involving movement of gaseous species similar to diffusion is effusion, the escape of gas molecules through a tiny hole such as a pinhole in a balloon into a vacuum (Figure 2). Although diffusion and effusion rates both depend on the molar mass of the gas involved, their rates are not equal; however, the ratios of their rates are the same. Figure 2. Diffusion occurs when gas molecules disperse throughout a container. Effusion occurs when a gas passes through an opening that is smaller than the mean free path of the particles, that is, the average distance traveled between collisions. Effectively, this means that only one particle passes through at a time. If a mixture of gases is placed in a container with porous walls, the gases effuse through the small openings in the walls. The lighter gases pass through the small openings more rapidly (at a higher rate) than the heavier ones (Figure 3). In 1832, Thomas Graham studied the rates of effusion of different gases and formulated Graham’s law of effusion: The rate of effusion of a gas is inversely proportional to the square root of the mass of its particles: This means that if two gases A and B are at the same temperature and pressure, the ratio of their effusion rates is inversely proportional to the ratio of the square roots of the masses of their particles: Figure 3. A balloon filled with air (the blue one) remains full overnight. A balloon filled with helium (the green one) partially deflates because the smaller, light helium atoms effuse through small holes in the rubber much more readily than the heavier molecules of nitrogen and oxygen found in air. (credit: modification of work by Mark Ott) Example 1Applying Graham’s Law to Rates of Effusion Solution
Using molar masses: Hydrogen effuses four times as rapidly as oxygen. Check Your Learning Here’s another example, making the point about how determining times differs from determining rates. Example 2Effusion Time Calculations Solution and combine it with Graham’s law: To get: Noting that amount of A = amount of B, and solving for time for Ne: and substitute values: Finally, solve for the desired quantity: Note that this answer is reasonable: Since Ne is lighter than Xe, the effusion rate for Ne will be larger than that for Xe, which means the time of effusion for Ne will be smaller than that for Xe. Check Your Learning Finally, here is one more example showing how to calculate molar mass from effusion rate data. Example 3Determining Molar Mass Using Graham’s Law Solution Plug in known data: Solve: The gas could well be CH4, the only gas with this molar mass. Check Your Learning Use of Diffusion for Nuclear Energy Applications: Uranium EnrichmentGaseous diffusion has been used to produce enriched uranium for use in nuclear power plants and weapons. Naturally occurring uranium contains only 0.72% of 235U, the kind of uranium that is “fissile,” that is, capable of sustaining a nuclear fission chain reaction. Nuclear reactors require fuel that is 2–5% 235U, and nuclear bombs need even higher concentrations. One way to enrich uranium to the desired levels is to take advantage of Graham’s law. In a gaseous diffusion enrichment plant, uranium hexafluoride (UF6, the only uranium compound that is volatile enough to work) is slowly pumped through large cylindrical vessels called diffusers, which contain porous barriers with microscopic openings. The process is one of diffusion because the other side of the barrier is not evacuated. The 235UF6 molecules have a higher average speed and diffuse through the barrier a little faster than the heavier 238UF6 molecules. The gas that has passed through the barrier is slightly enriched in 235UF6 and the residual gas is slightly depleted. The small difference in molecular weights between 235UF6 and 238UF6 only about 0.4% enrichment, is achieved in one diffuser (Figure 4). But by connecting many diffusers in a sequence of stages (called a cascade), the desired level of enrichment can be attained. Figure 4. In a diffuser, gaseous UF6 is pumped through a porous barrier, which partially separates 235UF6 from 238UF6 The UF6 must pass through many large diffuser units to achieve sufficient enrichment in 235U. The large scale separation of gaseous 235UF6 from 238UF6 was first done during the World War II, at the atomic energy installation in Oak Ridge, Tennessee, as part of the Manhattan Project (the development of the first atomic bomb). Although the theory is simple, this required surmounting many daunting technical challenges to make it work in practice. The barrier must have tiny, uniform holes (about 10–6 cm in diameter) and be porous enough to produce high flow rates. All materials (the barrier, tubing, surface coatings, lubricants, and gaskets) need to be able to contain, but not react with, the highly reactive and corrosive UF6. Because gaseous diffusion plants require very large amounts of energy (to compress the gas to the high pressures required and drive it through the diffuser cascade, to remove the heat produced during compression, and so on), it is now being replaced by gas centrifuge technology, which requires far less energy. A current hot political issue is how to deny this technology to Iran, to prevent it from producing enough enriched uranium for them to use to make nuclear weapons. Key Concepts and SummaryGaseous atoms and molecules move freely and randomly through space. Diffusion is the process whereby gaseous atoms and molecules are transferred from regions of relatively high concentration to regions of relatively low concentration. Effusion is a similar process in which gaseous species pass from a container to a vacuum through very small orifices. The rates of effusion of gases are inversely proportional to the square roots of their densities or to the square roots of their atoms/molecules’ masses (Graham’s law). Key EquationsChemistry End of Chapter Exercises
Glossarydiffusionmovement of an atom or molecule from a region of relatively high concentration to one of relatively low concentration (discussed in this chapter with regard to gaseous species, but applicable to species in any phase)effusiontransfer of gaseous atoms or molecules from a container to a vacuum through very small openingsGraham’s law of effusionrates of diffusion and effusion of gases are inversely proportional to the square roots of their molecular massesmean free pathaverage distance a molecule travels between collisionsrate of diffusionamount of gas diffusing through a given area over a given timeSolutionsAnswers to Chemistry End of Chapter Exercises 1. 4.2 hours 3. Effusion can be defined as the process by which a gas escapes through a pinhole into a vacuum. Graham’s law states that with a mixture of two gases A and B: . Both A and B are in the same container at the same temperature, and therefore will have the same kinetic energy:
5. F2, N2O, Cl2, H2S 7. 1.4; 1.2 9. 51.7 cm What factors affect diffusion across a membrane?The rate of diffusion is affected by the concentration gradient, membrane permeability, temperature, and pressure. Diffusion takes place as long as there is a difference between the concentrations of a substance across a barrier.
How does membrane permeability influence the transport of materials across a cell membrane?Selective permeability of the cell membrane refers to its ability to differentiate between different types of molecules, only allowing some molecules through while blocking others. Some of this selective property stems from the intrinsic diffusion rates for different molecules across a membrane.
What membrane acts as a barrier to some molecules while allowing others to pass through?Cell membranes serve as barriers and gatekeepers. They are semi-permeable, which means that some molecules can diffuse across the lipid bilayer but others cannot. Small hydrophobic molecules and gases like oxygen and carbon dioxide cross membranes rapidly.
What acts as a barrier to diffusion into and out of a cell?Most biological molecules are unable to diffuse through the phospholipid bilayer, so the plasma membrane forms a barrier that blocks the free exchange of molecules between the cytoplasm and the external environment of the cell.
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