In the previous module, we examined intermolecular forces and their impact on physical properties like vapor pressure. Here, we will begin looking at phase diagrams to examine the phase and phase transitions at various temperatures and pressures.
In the previous module, the variation of a liquid’s equilibrium vapor pressure with temperature was described. Considering the definition of boiling point, plots of vapor pressure versus temperature represent how the boiling point of the liquid varies with pressure. Also described was the use of heating and cooling curves to determine a substance’s melting (or freezing) point. Making such measurements over a wide range of pressures yields data that may be presented graphically as a phase diagram. A phase diagram combines plots of pressure versus temperature for the liquid-gas, solid-liquid, and solid-gas phase transition equilibria of a substance. These diagrams indicate the physical states that exist under specific conditions of pressure and temperature, and also provide the pressure dependence of the phase-transition temperatures (melting points, sublimation points, boiling points). A typical phase diagram for a pure substance is shown in Figure 1.
To illustrate the utility of these plots, consider the phase diagram for water shown in Figure 2.
We can use the phase diagram to identify the physical state of a sample of water under specified conditions of pressure and temperature. For example, a pressure of 50 kPa and a temperature of −10 °C correspond to the region of the diagram labeled “ice.” Under these conditions, water exists only as a solid (ice). A pressure of 50 kPa and a temperature of 50 °C correspond to the “water” region—here, water exists only as a liquid. At 25 kPa and 200 °C, water exists only in the gaseous state. Note that on the H2O phase diagram, the pressure and temperature axes are not drawn to a constant scale in order to permit the illustration of several important features as described here.
The curve BC in Figure 2 is the plot of vapor pressure versus temperature as described in the previous module. This “liquid-vapor” curve separates the liquid and gaseous regions of the phase diagram and provides the boiling point for water at any pressure. For example, at 1 atm, the boiling point is 100 °C. Notice that the liquid-vapor curve abruptly terminates at a temperature of 374 °C and a pressure of 218 atm, indicating that water cannot exist as a liquid above this temperature, regardless of the pressure. The physical properties of water under these conditions are intermediate between those of its liquid and gaseous phases. This unique state of matter is called a supercritical fluid.
The solid-vapor curve, labeled AB in Figure 2, indicates the temperatures and pressures at which ice and water vapor are in equilibrium. These temperature-pressure data pairs correspond to the sublimation, or deposition, points for water. If we could zoom in on the solid-gas line in Figure 2, we would see that ice has a vapor pressure of about 0.20 kPa at −10 °C. Thus, if we place a frozen sample in a vacuum with a pressure less than 0.20 kPa, ice will sublime. This is the basis for the “freeze-drying” process often used to preserve foods, such as the ice cream shown in Figure 3.
The solid-liquid curve labeled BD shows the temperatures and pressures at which ice and liquid water are in equilibrium, representing the melting/freezing points for water. Note that this curve exhibits a slight negative slope (greatly exaggerated for clarity), indicating that the melting point for water decreases slightly as pressure increases. Water is an unusual substance in this regard, as most substances exhibit an increase in melting point with increasing pressure. But water, as we have seen previously, is more dense in the liquid phase than the solid phase, leading to this negative slope on the phase diagram. This behavior is partly responsible for the movement of glaciers, like the one shown in Figure 4. The bottom of a glacier experiences an immense pressure due to its weight that can melt some of the ice, forming a layer of liquid water on which the glacier may more easily slide.
The point of intersection of all three curves is labeled B in Figure 2. At the pressure and temperature represented by this point, all three phases of water coexist in equilibrium. This temperature-pressure data pair is called the triple point. At pressures lower than the triple point, water cannot exist as a liquid, regardless of the temperature.
Determining the State of Water
Using the phase diagram for water given in Figure 2, determine the state of water at the following temperatures and pressures:
- −10 °C and 50 kPa
- 25 °C and 90 kPa
- 50 °C and 40 kPa
- 80 °C and 5 kPa
- −10 °C and 0.3 kPa
- 50 °C and 0.3 kPa
Using the phase diagram for water, we can determine that the state of water at each temperature and pressure given are as follows:
(a) solid; (b) liquid; (c) liquid; (d) gas; (e) solid; (f) gas.
Check Your Learning
What phase changes can water undergo as the temperature changes if the pressure is held at 0.3 kPa? If the pressure is held at 50 kPa?
At 0.3 kPa: s → g at −58 °C.
At 50 kPa: s → ℓ at 0 °C and ℓ → g at 78 °C.
Consider the phase diagram for carbon dioxide shown in Figure 5 as another example. The solid-liquid curve exhibits a positive slope, indicating that the melting point for CO2 increases with pressure as it does for most substances (water being a notable exception as described previously). Notice that the triple point is well above 1 atm, indicating that carbon dioxide cannot exist as a liquid under ambient pressure conditions. Instead, cooling gaseous carbon dioxide at 1 atm results in its deposition into the solid state. Likewise, solid carbon dioxide does not melt at 1 atm pressure but instead sublimes to yield gaseous CO2. Finally, notice that the critical point for carbon dioxide is observed at a relatively modest temperature and pressure in comparison to water.
Determining the State of Carbon Dioxide
Using the phase diagram for carbon dioxide shown in Figure 5, determine the state of CO2 at the following temperatures and pressures:
- 243 K and 20 bar
- 213 K and 10 bar
- 213 K and 1 bar
- 293 K and 100 bar
- 273 K and 1 bar
- 293 K and 1 bar
Using the phase diagram for carbon dioxide provided, we can determine that the state of CO2 at each temperature and pressure given are as follows:
(a) liquid; (b) solid; (c) gas; (d) liquid; (e) gas; (f) gas.
Check Your Learning
Determine the phase changes carbon dioxide undergoes when its temperature is varied, thus holding its pressure constant at 15 bar? At 5 bar? At what approximate temperatures do these phase changes occur? (Hint: the triple point of CO2 is 217 K and 5.3 bar.)
at 15 bar: s → ℓ at ~220 K, ℓ → g at ~250 K.
at 5 bar: s → g at 215 K.
If we place a sample of water in a sealed container at 25 °C, remove the air, and let the vaporization-condensation equilibrium establish itself, we are left with a mixture of liquid water and water vapor at a pressure of 0.03 atm. A distinct boundary between the more dense liquid and the less dense gas is clearly observed. As we increase the temperature, the pressure of the water vapor increases, as described by the liquid-gas curve in the phase diagram for water (Figure 2), and a two-phase equilibrium of liquid and gaseous phases remains. At a temperature of 374 °C, the vapor pressure has risen to 218 atm, and any further increase in temperature results in the disappearance of the boundary between liquid and vapor phases. All of the water in the container is now present in a single phase whose physical properties are intermediate between those of the gaseous and liquid states. This phase of matter is called a supercritical fluid, and the temperature and pressure above which this phase exists is the critical point (Figure 6). Above its critical temperature, a gas cannot be liquefied no matter how much pressure is applied. The pressure required to liquefy a gas at its critical temperature is called the critical pressure. The critical temperatures and critical pressures of some common substances are given in Table 1.
|Substance||Critical Temperature (K)||Critical Pressure (atm)|
Like a gas, a supercritical fluid will expand and fill a container, but its density is much greater than typical gas densities, typically being close to those for liquids. Similar to liquids, these fluids are capable of dissolving nonvolatile solutes. They exhibit essentially no surface tension and very low viscosities, however, so they can more effectively penetrate very small openings in a solid mixture and remove soluble components. These properties make supercritical fluids extremely useful solvents for a wide range of applications. For example, supercritical carbon dioxide has become a very popular solvent in the food industry, being used to decaffeinate coffee, remove fats from potato chips, and extract flavor and fragrance compounds from citrus oils. It is nontoxic, relatively inexpensive, and not considered to be a pollutant. After use, the CO2 can be easily recovered by reducing the pressure and collecting the resulting gas.
The Critical Temperature of Carbon Dioxide
If we shake a carbon dioxide fire extinguisher on a cool day (18 °C), we can hear liquid CO2 sloshing around inside the cylinder. However, the same cylinder appears to contain no liquid on a hot summer day (35 °C). Explain these observations.
On the cool day, the temperature of the CO2 is below the critical temperature of CO2, 304 K or 31 °C (Table 1), so liquid CO2 is present in the cylinder. On the hot day, the temperature of the CO2 is greater than its critical temperature of 31 °C. Above this temperature no amount of pressure can liquefy CO2 so no liquid CO2 exists in the fire extinguisher.
Check Your Learning
Ammonia can be liquefied by compression at room temperature; oxygen cannot be liquefied under these conditions. Why do the two gases exhibit different behavior?
The critical temperature of ammonia is 405.5 K, which is higher than room temperature. The critical temperature of oxygen is below room temperature; thus oxygen cannot be liquefied at room temperature.
Chemistry in Real Life: Decaffeinating Coffee Using Supercritical CO2
Coffee is the world’s second most widely traded commodity, following only petroleum. Across the globe, people love coffee’s aroma and taste. Many of us also depend on one component of coffee—caffeine—to help us get going in the morning or stay alert in the afternoon. But late in the day, coffee’s stimulant effect can keep you from sleeping, so you may choose to drink decaffeinated coffee in the evening.
Since the early 1900s, many methods have been used to decaffeinate coffee. All have advantages and disadvantages, and all depend on the physical and chemical properties of caffeine. Because caffeine is a somewhat polar molecule, it dissolves well in water, a polar liquid. However, since many of the other 400-plus compounds that contribute to coffee’s taste and aroma also dissolve in H2O, hot water decaffeination processes can also remove some of these compounds, adversely affecting the smell and taste of the decaffeinated coffee. Dichloromethane (CH2Cl2) and ethyl acetate (CH3CO2C2H5) have similar polarity to caffeine, and are therefore very effective solvents for caffeine extraction, but both also remove some flavor and aroma components, and their use requires long extraction and cleanup times. Because both of these solvents are toxic, health concerns have been raised regarding the effect of residual solvent remaining in the decaffeinated coffee.
Supercritical fluid extraction using carbon dioxide is now being widely used as a more effective and environmentally friendly decaffeination method (Figure 7). At temperatures above 304.2 K and pressures above 7376 kPa, CO2 is a supercritical fluid, with properties of both gas and liquid. Like a gas, it penetrates deep into the coffee beans; like a liquid, it effectively dissolves certain substances. Supercritical carbon dioxide extraction of steamed coffee beans removes 97−99% of the caffeine, leaving coffee’s flavor and aroma compounds intact. Because CO2 is a gas under standard conditions, its removal from the extracted coffee beans is easily accomplished, as is the recovery of the caffeine from the extract. The caffeine recovered from coffee beans via this process is a valuable product that can be used subsequently as an additive to other foods or drugs.
The temperature and pressure conditions at which a substance exists in solid, liquid, and gaseous states are summarized in a phase diagram for that substance. Phase diagrams are combined plots of three pressure-temperature equilibrium curves: solid-liquid, liquid-gas, and solid-gas. These curves represent the relationships between phase-transition temperatures and pressures. The point of intersection of all three curves represents the substance’s triple point—the temperature and pressure at which all three phases are in equilibrium. At pressures below the triple point, a substance cannot exist in the liquid state, regardless of its temperature. The terminus of the liquid-gas curve represents the substance’s critical point, the pressure and temperature above which a liquid phase cannot exist.
- critical point
- temperature and pressure above which a gas cannot be condensed into a liquid
- phase diagram
- pressure-temperature graph summarizing conditions under which the phases of a substance can exist
- supercritical fluid
- substance at a temperature and pressure higher than its critical point; exhibits properties intermediate between those of gaseous and liquid states
- triple point
- temperature and pressure at which the vapor, liquid, and solid phases of a substance are in equilibrium
- What phase changes will take place when water is subjected to varying pressure at a constant temperature of 0.005 °C? At 40 °C? At −40 °C?
- From the phase diagram for carbon dioxide in Figure 5, determine the state of CO2 at:
- 225 K and 10 bar
- 210 K and 20 bar
- 283 K and 1 bar
- 233 K and 5 bar
- Determine the phase changes that carbon dioxide undergoes as the pressure changes if the temperature is held at 223 K? If the temperature is held at 233 K? At 293 K? (See the phase diagram in Figure 5.)
- Consider a cylinder containing a mixture of liquid carbon dioxide in equilibrium with gaseous carbon dioxide at an initial pressure of 65 atm and a temperature of 20 °C. Sketch a plot depicting the change in the cylinder pressure with time as gaseous carbon dioxide is released at constant temperature.
- Dry ice, CO2(s), does not melt at atmospheric pressure. It sublimes at a temperature of 195 K. What is the lowest pressure at which CO2(s) will melt to give CO2(ℓ)? At approximately what temperature will this occur? (See Figure 5 for the phase diagram.)
- For CO2 the critical temperature is 31.1 ºC and the critical pressure is 73 atm. These data imply that CO2 can be liquefied under what set of conditions?
- 31.1 ºC and 72.0 atm
- 32.0 ºC and 72.0 atm
- 30.0 ºC and 73.0 atm
- 32.0 ºC and 73.0 atm
- 32.0 ºC and 74.0 atm
- If a severe storm results in the loss of electricity, it may be necessary to use a clothesline to dry laundry. In many parts of the country in the dead of winter, the clothes will quickly freeze when they are hung on the line. If it does not snow, will they dry anyway? Explain your answer.
- Is it possible to liquefy nitrogen at room temperature (about 25 °C)? Is it possible to liquefy sulfur dioxide at room temperature? Explain your answers.
- Elemental carbon has one gas phase, one liquid phase, and two different solid phases, as shown in the phase diagram:
- On the phase diagram, label the gas and liquid regions.
- Graphite is the most stable phase of carbon at normal conditions. On the phase diagram, label the graphite phase.
- If graphite at normal conditions is heated to 2500 K while the pressure is increased to 1010 Pa, it is converted into diamond. Label the diamond phase.
- Circle each triple point on the phase diagram.
- In what phase does carbon exist at 5000 K and 108 Pa?
- If the temperature of a sample of carbon increases from 3000 K to 5000 K at a constant pressure of 106 Pa, which phase transition occurs, if any?
- At low pressures and 0.005 °C, the water is a gas. As the pressure increases to ~0.6 kPa, the water becomes a solid; as the pressure increases still more, it becomes a liquid. At 40 °C, water at low pressure is a vapor; at pressures higher than ~10 kPa, it converts into a liquid. At −40 °C, water goes from a gas to a solid as the pressure increases above very low values.
- (a) liquid; (b) solid; (c) gas; (d) gas
- The phase changes for all the given temperatures are gas at low pressure to liquid as pressure is increased.
- 5 bar, 215 K
- Yes, ice will sublime, although it may take it several days. Ice has a small vapor pressure, and some ice molecules form gas and escape from the ice crystals. As time passes, more and more solid converts to gas until eventually the clothes are dry.
- Nitrogen cannot be liquid at room temperature because its critical temperature is 126 K. Sulfur dioxide can be liquefied at room temperature because its critical temperature is 430 K.
- (a) (b)
(e) liquid phase; (f) sublimation
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