Solids, Liquids, and Gases

By Robert A. Edwards We usually think of oxygen as a gas, but oxygen will form a liquid and even a solid if it is cooled down enough (or compressed enough). This is also true of other gases as well, including the nitrogen and argon found in the air that we breathe. For example, argon (0.94% of the air) forms a liquid when cooled to 185.7C and then becomes a solid below -189.2C. The differences between solids, liquids, and gases are illustrated by the simple model shown in Figure 17.1. The molecules (or atoms) are touching one another in solids. Liquid, on the other hand, have a small amount of empty space between the molecules. Gases have large amounts of empty space between molecules which are travelling through space. The gas molecules exert pressure on the walls of the container by colliding with the walls.

Figure 17.1The left hand panel shows a model of a solid with spherical atoms (or molecules) touching one another. The central panel shows a model of a liquid with some atoms touching one another but small spaces and holes between molecules are present. The right hand panel shows a model of a gas with atoms bouncing around in mostly empty space.

Example Using the model in Figure 17.1, describe how the liquid water exerts pressure on the sides of an open graduated cylinder which is filled with water? ANSWER As a gaseous air molecule strikes the top water in the cylinder it compresses the molecule which it struck (call that water molecule-X) very slightly which exerts force on any molecule touching water molecule-X. This force is then transferred through a sequence of molecules which were touching one another to the wall of the cylinder. If water molecule-X happened to have a space next to it when it was struck by the air molecule, the water molecule-X might move into the space, but that also transfers the pressure, because it jostles other molecules as it moves into the space.

Example The density of solid argon near 0k is about 1.77 g/cm3 (Dobbs ER, BF Friggins, and GO Jones, Properties of solid argon, del nuovo cimento, 1958, supplemento IX (X), 32-35). What is the volume and radius of an argon atom? Assume that the argon atoms in a solid undergo closest packing (as is illustrated in Figure 17.1). (Hint it can be shown geometrically that for closet packing the spheres occupy 74.0% of the space.) ANSWER Volume (atom + empty space) in the bulk per mole of atoms 39.948 g/mol / 1.77 g/cm3 = 22.57 cm3/mol (1L/1000cm3) = 0.02257 L/mol Volume & radius actually occupied by the hard sphere atoms is only 74.0%: 0.02257 L/mol 0.740 = 0.0167 L/mol 0.0167 10-3 m3/mol / 6.02 1023 molecules/mol = 2.77 10-26 m3/molecule 2.77 10-26 m3/molecule = (4/3)r3 r = 1.88 10-9 m By increasing the pressure on a gas in a closed container compresses the gas into a smaller volume. Boyles Law (VmP = k) mathematically describes the change in molar volume as pressure increases. The same mathematically relationship between volume and pressure is found in the ideal gas law (PVm = RT). These laws are a fairly good description of how the volume of most

gases at relatively low pressures (<1 atm) respond when compressed. However, these laws are a poor description of the pressures above 10 atmospheres. Liquids and solids also decrease their volume when compressed at room temperature, but not nearly as much as for a gas. Qualitatively the models in Figure 17.1 helps us to understand this behavior, because there is very little space to squeeze out when a liquid or solid are compressed; whereas, for a gas there is a lot of space between the atoms. For solids and liquids, the equation used to express the volume as a function of pressure (Vm = Vmo {1-P}), has a constant () which is called the isothermal compressibility. This constant is positive so the negative sign in the equation implies that the volume decreases with increased pressure. This equation does not include an explicit description However, the of how the volume will change as temperature changes.

isothermal compressibility is a constant only at a fixed temperature and in many cases tables can be found of the isothermal compressibility at many temperatures. There are several kinds of attractive forces between molecules which pull the molecules of a solid together to form a crystal or a tightly packed amorphous solid. These attractive forces are also operating in the liquid phase but the temperature is high enough that the molecules roll around each other so that there is some empty space between the molecules. In the gaseous phase most of the molecules are not in contact with one another; instead, they are bouncing around in the large volume of the container but the do exert small attractive forces on one another. The ideal gas law is not a good description of the behavior of gases at moderate to high pressures (>10 atm). The attractive forces between gas molecules as well as the volume occupied by the hard spheres cause them to deviate from ideal behavior. Van der Waals modified the ideal gas law to take account for

these two effects and came up with the first equation below. These parameters are different for different gases. volume when pressure and temperature are known.

Two Van der

Waals parameters designated a and b are included in the equations. The second equation, which is derived for the first one with a small approximation, allows the calculation of

P = Vm
Where:

RT (Vm-b)

a (Vm)2 a RT

RT + b P

a is a parameter for the attractive forces between gas molecules. b is a parameter which accounts for the volume occupied by the hard spheres called the Van der Waals volume. Example How many moles of oxygen would be present in an M60 oxygen cylinder which has a volume of 164 L and is filled to a pressure of 2200 psi at room temperature? Assume (a) the oxygen is an ideal gas and (b) that the oxgyen is a Van der Waals gas with a=1.378 L2atm/mol2 and b = 0.13038 L/atm. ANSWER 2200 psi / (14.69595 psi/atm) = 149.7 atm Ideal Gas: n = PV/RT = 149.7 atm 164 L/ 0.08206 Latm/mol K 298.15K = 1003 moles Van der Waals Gas: Vm 0.08206 Latm/mol K 298.15K/149.7 atm + 0.13038 L/atm 1.378 L2atm/mol2 /0.08206 Latm/mol K 298.15K Vm 0.2375 L n = V / Vm = 690.5 moles

The Van der Waals constants for the inert gases are tabulated on Table 17.1. They show that the Van der Waals volume increases as the atoms get larger from helium to xenon. In general, the attractive forces also get stronger as the atoms get larger. The attractive forces operating between these atoms are induced dipole induced dipole (London dispersion) force. As two atoms approach one another there may be a temporary fluctuation of the electron cloud in one of the atoms which produces a temporary dipole moment (slight positive charge on one side and slight negative charge on the other). The electron cloud in the other atoms instantaneously fluctuates in the opposite direction so that there is an electrical attraction between the two atoms. Table 17.1 Van der Waals parameters for the inert gases from Weast. R. C. (Ed.), Handbook of Chemistry and Physics (53rd Edn.), Cleveland:Chemical Rubber Co., 1972. Helium a (L2atm/mol2) b (L/mol) 0.03457 0.0237 Neon 0.2135 0.01709 Argon 1.363 0.03219 Xenon 4.250 0.05105

The amount of this interaction between induced dipoles depends upon how large and flexible the electron clouds are so that they can shift. The polarizability of any atom or molecule is a measure of how easily it electron cloud can be shifted. Xenon is a large atom with its valence electrons far from the nucleus and more able to be polarized than the other atoms in this series. Hence, Xenon has a greater polarizability than the other inert gas atoms. For molecules with permanent dipole moments there are also dipole-dipole and dipole-induced dipole attractive forces between them, even in the gas phase. Thus the Van de Waals parameters in Table 17.2 show greater attraction between water molecules than between ethane molecules, even though they have about the same size. All three types of Van der Waals forces (dipole-

dipole, dipole-induced dipole, and induced dipole induced dipole) exist between water molecules; whereas, between the only type of Van der Waals forces between ethane molecules are induced dipole induced dipole forces. Table 17.2 Van der Waals parameters for several small molecules from Weast. R. C. (Ed.), Handbook of Chemistry and Physics (53rd Edn.), Cleveland:Chemical Rubber Co., 1972. Water a (L2atm/mol2) b (L/mol) 5.536 0.03049 Ammonia 4.225 0.03707 Methane 2.283 0.04278 Ethane 5.562 0.0638

Example Describe the dipole induced dipole forces that occur between water molecules in the gas phase. ANSWER Water molecules have a permanent dipole in which the oxygen is slightly negative and the hydrogen atoms are slightly positive. dipole in the neighbor is formed. When this dipole on one water molecule causes a shift in the electron cloud of a neighboring water molecule then an induced Because this induced dipole has an orientation such that the slight negative charge is close to the positive of the permanent dipole, there is an attractive force between the molecules. Van der Waals constants are determined by fitting the experimental pressure versus volume graph at constant temperature (referred to as a PV isotherm) of each gas to the Van der Waals equation. This yields a Van der Waals volume (b) that is larger than the volume of the hard sphere atoms calculated from the solid phase. For example, The VdWs volume of argon is 0.03219 L/mol; whereas, the volume occupied by the atoms was 0.0167 L/mol as calculated in

the example above. So the VdWs volume is about twice the actual volume of the sheres in a solid. Part of the reason for this is that the atoms are not completely hard spheres. Instead, they are partially soft spheres that can overlap slightly in the solid phase. It is common to calculate the radius of the spheres in the solid phase as was done in the earlier example and call the Van der Waals radius (i.e. the Van der Waals radius of argon is 188 nm as calculated in the example above). This can be confusing because the Van der Waals radius indicates how closely atoms can come together in condensed phases like the solid. It is not calculated from the Van der Waals volume but from the density of the solid.

PRACTICE PROBLEMS 1. The density of argon liquid at its melting point is 1.41 g/cm3 (calculated from equation in Goldman, K and NG Scrase, Densities of saturated liquid argon, Physica, 1969, 45, 1-11). Calculate the amount of empty space in argon liquid at its melting point. 2. Why do attractive forces between atoms reduce the pressure exerted on the walls of a container by a gas?

3. The density of H2O(l) at 0C is 1.0454 g /cm3 under 1000. atm of pressure. (a) How well does the equation Vm = a + bT + cP predict the density value above? (Hint: calculate the percentage error between the actual and predicted value.) (b) Assuming that H2O(l) under these conditions has 30% vacant space, calculate the Van der Waals' radius of water (assuming that H2O molecules are spheres)

4. Use calculus to determine the pressure change inside a cylinder with 3.200 kg of oxygen gas at 298.00K in a volume of 45.00 L in each case below. (Assume that O2(g) is an ideal gas so that P = nRT/V.) a) A decrease of 0.010 moles in the number of moles of gas. b) A decrease of 0.010K in the temperature. c) A decrease of 0.010 L in the volume. 5. Consider a cylinder containing 4.48 kg of ethylene gas (C2H4) in a volume of 45.0 L, which gives a pressure of 50.0 atm. at 20C. For ethylene the VdWs parameters are a=4.471 L2atm/mol2 and b=0.05714 L/mol. (a) What would the volume be if this were (i) an ideal gas or (ii) a VdWs gas. (b) Is this gas closer to an ideal gas or a VdWs gas? (c) Explain, at a molecular level, why the gas pressure increases then decreases if a VdWs gas is compressed. 6. In liquid water with oxygen in it (i.e., O2(aq)), which of the Van der Waals' forces are present between the molecules listed below? Why are liquids more compressible than solids? (a) Two water molecules. (b) A water molecule and an oxygen molecule.

ANSWERS to PRACTICE PROBLEMS 1. The density of argon liquid at its melting point is 1.41 g/cm3 (calculated from equation in Goldman, K and NG Scrase, Densities of saturated liquid argon, Physica, 1969, 45, 1-11). Calculate the amount of empty space in argon liquid at its melting point. Volume in the bulk per mole of atoms 39.948 g/mol / 1.41 g/cm3 = 28.33 cm3/mol (1L/1000cm3) = 0.02833 L/mol The volume actually occupied by the atoms 0.01825 L/mol (from the calculation on solid argon in the example) Therefore: 100 (0.1825/.02833) = 64.4% of the volume is occupied by atoms 100-64.4 = 35.6% is empty space 2. Why do attractive forces between atoms reduce the pressure exerted on the walls of a container by a gas? As a molecule approaches the wall it is attracted back into the bulk by the gas molecules behind it so it will slow down slightly and thus hit the wall with less force. Pressure is force per unit area, so there will be less pressure on the wall.