Chapter 10 Liquids and Solids

Last semester we looked at the simplest phase of matter, gases. This was simple because the individual molecules had very little interaction with each other. This semester will get more complicated and look at liquids and solids. These states are more complicated because in these phases the individual molecules interact with each other. First we must learn what the forces are and how they interact, then we can begin to understand how these forces shape the liquids and solid state of matter. If you think about water you may conclude that the liquid and the solid state are more closely related than the liquid and gaseous states. The density of solid and liquid waters are much the same and are very different from that of water (g). Liquid and solid water are both non-compressible, while gaseous water is. We will refer to solids and liquids as condensed states . 10.1 Intermolecular Forces In looking at molecules we were dealing with forces within the molecule. We call these forces intramolecular forces (within the molecule). In looking at condensed states we will be dealing with intermolecular forces (forces between molecules). These forces may be ionic or covalent or some other weaker interactions that I will describe shortly. It is important to remember that in the transition we will talk about here (S-G, I-g, etc), the molecules remain intact. Thus we are not changing the chemical bonds between atoms within the molecule, but we are changing how each molecule interacts with its neighbor. Thus we are dealing with physical change, not chemical change. For instance in ice we have water molecules locked into a crystal where they vibrate in place. When we change to liquid the molecules vibrate and rotate around but still interact with each other. Finally in the gas form they vibrate rotate and translate freely because they have virtually no interactions with their neighbors. We have changed forms, but in each case we were dealing with water molecules, Charge-Charge or Electrostatic Forces Actually learned about these last semester, Opposite charges attract, like charges repel. One of the strongest forces ar the molecular level, and also one of the longest range forces Dipole-dipole forces Remember form chapter 8 that molecules with polar bonds often, but not always, act like they have + and negative charges built into the molecule. The way we normally observe this is by watching if they orient in an electric field. (Put water in an electric field on board and show its orientation) The electric field they orient to can be on another molecule, hence water molecules will orient like this.... Typically you will see molecule with dipole moments lining out so the + and - are aligned in the condensed state. This is called dipole-dipole attraction.

3 Dipole forces like this are generally <1% as strong as covalent or ionic bonds. They are also very distance dependent and get much smaller with distance. Thus is the gas phase, where there is lots of distance between atoms, dipole-dipole interaction are virtually nil. Dipole-dipole interactions in molecules involving H and an electronegative atom like N, O, or F are especially strong because of the large difference in electronegativity and because the H is such a small atom that the dipole of one molecule can get very close to the dipole of another. Dipole interactions involving these atoms are given a special name hydrogen bonds to designate this particularly strong dipole-dipole interaction. Hydrogen bonding is a major reason that water acts like it does (show water h bonding) and has its particularly high melting and boiling points. and it very important in many biological processes. London dispersion forces or van der Waals forces Even molecules that do not have dipole still exert a small force on each other. (This includes the noble gases as well!) These forces are called London dispersion forces. Lets explain these forces with a pair of helium atoms. Our usual assumption is that the electrons are uniformly distributed around the atom, right? The idea here is that at any particular instant the electron in 1 He are slopping around in their orbital and may not be 100% evenly distributed, so, for an instant, the molecule has a dipole. The dipole in one atom give a polar environment so the neighboring atom will respond by having its electrons slosh accordingly, and it picks up a dipole for an instant. Thus we have an induced dipole. This interaction is very low energy and very short range. It is more predominant in the larger atoms because the larger the electron cloud, the easier it is to temporarily distort the electrons. London forces are also present in molecules as well as atoms so it is seen everywhere. 10.2 The liquid state What are some of the properties of the liquid state 1. Low compressibility (at least compared to gas 2. Lack of rigidity 3. High density (compared to a gas) Some other properties you may not think about that arise from 2 different molecular interactions: adhesion - the attraction between molecules of the liquid, and cohesion- the attraction between the molecules of the liquids and the molecules of the surroundings. 1. Surface Tension (Maximum cohesive force/minimum adhesive force) -Droplets assume spherical shape -Why intermolecular forces, attracted to each other but not to surface maximize contacts with each other and minimize contacts with surface. -Results in Surface tension, the resistance to increase in surface area (because this means less

4 - Moe polar liquids, more attractive forces, higher surface tension 2. Capillary action (Mix of cohesion and adhesion) - Water sucked into paper towel, or up a narrow tube Balance between cohesive forces and adhesive forces Cohesive forces - attraction between liquid molecules Adhesive forces - attraction of liquid to surface How high water goes is balance 3. Viscosity (Max of cohesion) -How much liquid resists flow - Motor oil grades, shampoos, gas vs oil vs grease - more intermolecular forces more viscosity Structural models for liquids Bleep there is no good one! Gases are simple, lots of motion but little interaction so easy to model Solids are do-able. Lots of interaction but little motion Liquids moderate interaction, moderate motion, no good way to model. 10.3 Intro to structures and type of solids Lots of different ways to classify the structure, lets start with one you had in lab amorphous - lots of disorder in structure crystalline - highly regular arrangement of components Will concentrate on crystalline solids here because are easier to understand. There are important amorphous solids (like glass) but dont have a good handle on it structure that can teach at this level. The regular arrangement of atoms in crystalline compounds gives rise to the beautiful shapes of crystals (snow flakes, mineral crystals, etc. Positions of components in the crystalline solid usually represented as lattice a 3-D system of points that designate the position of the components (components may be atoms, ions or molecules) The smallest repeating unit of a lattice is called the unit cell Figure 10.9 shows a few of the simplest lattices. The crystal structure may be derived from arranging one lattice on top of another. X-ray Analysis of Solids How do we know that the crystals have the structure they do? Found by X-ray diffraction, that is shine X-ray light at the crystal and see how it bounces off. Look at figure 10.10. The whole idea is based on constructive and destructive interference. Lets sit at angle theta with respect to our crystal plane. Notice in case 1 the wave forms going to the second atom travel exactly two wavelength more. What happens if the distance between

5 the atoms is different or the angle is different? Wave out of phase, and cancel out. Without getting into the math, which is elementary geometry if you want to think about it we have the relationship n8 = 2dsin 2 This is called the Bragg equation. Essentially what we do is to shine X-rays at a crystal then look for all the angle places where X-rays appear around it. Can reconstruct distances between atoms form this. Problem 41 Use X-ray of 1.54D to look at a sample of silicon and see an angle of 14.22o for the first order reflection (n=1) 1(1.54D) =2d sin(14.22o) 1.54 = 2d(.2456) 1.54D/(2X.2456) =d; d=3.13D Types of crystalline Solids Make following on board as do this Types of solids Amorphous Crystalline Ionic Molecular Atomic Metallic Network Group 8A There are many types of crystalline solids. For instance we have talked many times about how NaCl is an ionic solid. That is it contains Na + anc Cl- ions these ions are arranged in the crystal to minimize repulsion and maximize attractions. On the other hand we know that Sugar is also crystalline, but it is made up of neutral molecules and does not contain ions. We know this because sugar solutions do not conduct electricity We differentiate between these two solids by calling them ionic solids vs molecular solids. Ionic solids have ions at the points of their lattice while molecular solids have molecules at the points in their lattice. Ice is what? Molecular solid with water molecules at the points of the lattice We also have atomic solids. These substances have atoms at the points of their lattice. Metals, diamond), graphite(C) ,boron, silicon are examples of elements that form atomic solids Atomic solids may be further classified as Metallic, network, and group 8a depending on special properties Metallic -delocalized covalent bonding in matrix (metallic element -metals)

6 network -directional covalent bonding (diamond, non-metals)) Group 8a- London dispersion forces hold together (inert gas solids) The different kinds of bonding in each lattice lead to the properties of the lattice At, Cu and C can all form atomic solids Group 8a, metallic and network, respectively Weak London forces in At means will melt easily (-189) Strong covalent diamond melts 3,500 Strong Ionic NaCl melt 1083 Delocalized bonding mean Cu will conduct electrically, C and At will not also Cu ductile and malleable, Diamond is hard and brittle With this as a general introduction, now lets look at the details 10.4 Structure and Bonding in metals So lets look at the metals first Figure 10.13-10.16 Properties of metals 1. Ductile, malleable 2. Conduct heat and electricity - both due to non-directional covalent bonding Picture as hard spheres all bonded equally in all directions Pack spheres to best use space closest packing Hexagonal arrays, hole on top of spheres. Like BBs in a box Second layer fits on top of holes in 1 st layer Note 3 rd layer can be arranged 2 ways , so either directly above 1st layer (aba arrangement - hexagonal closest packed array (hcp)-hexagonal unit cell 3rd layer offset from 1 st (triangle point opposite direction) (abc arrangement- cubic closest packed structure (ccp)- unit cell is cube so we are back to a face centered cubic lattice In both structure 1 sphere has 12 equivalent neighbors, 3-6-3 by plane The net number of spheres in a unit cell is important. Figuring it out can be a little tricky because need to split atoms if they are on the edge or corners Although it is hard to see. The cubic closest packed array gives a face centered cubic unit cell . Lets look at the atoms in this cell. In each face we have atom, 6 x =3 At each corner we have 1/4 atom 8 x 1/8 =1 So we have a net of 4 atoms in the unit cell. Now, for completeness how many atoms are there in a ... simple cubic lattice 1=8x1/8 Body centered lattice

7 2 = 8x 1/8 + 1 Most years I do not do the following page How is this useful? For instance it allows us to convert between atomic radii and densities For instance Nickel has an atomic radius of 136 pm (1.36 A) and packs into te closest packed cubic array. What is its density? Density is gram/volume. From teh molecule mass we know the mass of an atom. From the radius we known the volume of the atom Why cant we just divide one by the other? I lattice there is space between atoms, need to take into account So what we really need is to know how big the unit cell is for our volume and how many atoms are in it for the mass Lets do the easy one first. I just said a face centered cubic lattice contain 4 atoms. Therefor the mass of 1 lattice is : 4 x 58.696/mol x 1/6.022x1023 atom/mole = 3.90x10-22g Now what is the volume of that cell I just said the closest packed cubic array is a face centered lattice Therefore it looks like Figure 10.17.c If we know the radius of the sphere, then the diagonal across one face is 4r or 136pmx4 = 544pm What is the length of a side (remember your right triangles? Hypt2 = x2 + y2 5442 = x2 + x2 5442 = 2x2 5442/2=x2 1.48x105 = x2 385pm = x Now we have the side of a sphere, what is its volume? 385 x 385 x 385 = 5.69x107 pm3 So we have a density of 3.90x10-22 g/5.67x107 pm3 Lets et this into more reasonable units Lets convert pm3 to cm3 3.90x10-22 g/5.67x107 pm3 x (1012 pm/102cm)3 =6.85x10-30 x 1010 x 1010 x 1010 = 6.85 g/cm3 With a little thought you should be able to go the other way as well, i.e. density to radius

8 Return to useful info Aluminum, iron copper cobalt and nickel all for cubic close packed solids Mg and Zn form hexagonal closest packed arrays Ca and a few other metals can go either way Some metals do not go to closest packed array but fill in other lattices structure that are not so tightly packed. Why a metal uses the array it does is not well understood Bonding models in metals I mentioned earlier that metals use delocalized covalent bonding. What does this mean and how does it work? The easiest visualization of metallic bonding is that a metallic is made of a regular array of cations with a sea of valence electrons that move easily form one atoms to the next. This explains why metals conduct electricity, and why they conduct heat. Also because there are to bonds directed from one atom to the next, metals are both malleable and ductile because you can move atoms within the matrix relatively easily without breaking specific bonds The more detailed explanation of this idea is called the band model or molecular orbital model.. Remember in the molecular orbital of Li 2 we started with 2 atomic orbital of the same energy and combined them into 2 molecular orbital of widely spaced energy. In metals we have lots of adjacent atom interacting with each other so we have a blending of many equal energy atomic orbitals . In this blending we get an essential continuous band of extremely closely spaced energy levels or a a band of orbital that are not restricted to a single nucleus, but allow the electrons to move from one atoms to the next. Metal alloys- technically solutions! Because of the above delocalized bonding arrangement, it is relatively easy to introduce other metal atoms into a lattice of 1 kind of metal atom. This creates what is called an alloy An Alloy is a mixture of elements that has metallic properties. We have 2 types of alloys 1. Substitutional alloys- host metal atoms are replaced by another metal atom of similar size Brass 2/3 Cu 1/3 Zn (same size??_) Sterling silver 93% silver 7% copper pewter 85% Sn 7% Cu 6% Bi 2% Sb(antimony) Solder (67% Pb 33% Sn) Note: since no specific bonds, no specific ratio of elements 2. Interstitial alloys - atoms of second substance occupy interstices (holes) in the matrix Iron vs steel Iron pure Fe Steel - <2% C in interstitices

9 Picture 10.21 is real? Fe about 1.24 A radius C about .7 so I think it greatly overstates the case for clarity Note that the C will tend to have directional covalent bonds to the Fe and this will change the behavior of the material. Making it much stronger and harder. Hence we have Mild steels (<0.2% C Medium Steels (.2-.6% C) High Carbon steels (0.6-1.5% C) Can have both kind of alloys in a single substance. For instance bicycle frames have C, Si, Mn, Mo and Cr this is called an alloy steel, has both substitutional and interstitial atoms. 10.5 Carbon and Silicon: Network Atomic Solids and many other useful compounds Figure 10.22 Now let us look at network atomic solids. In particular let us compare and contrast the networks of Si and C since are so prevalent in out world. You can think of a network solid like a giant covalent molecule with standard covalent bonds between all the atoms. The nature of the interatomic covalent bond greatly influences the nature of the solid. Take, for instance, C. There are three forms of elemental C, diamond, graphite, and buckminsterfullerene or bucky balls. In a diamond you have sp3 hybridized single bonds from 1 atom to the next for form a matric like this Model of Diamond structure In contrast to the metallic state the covalent bonds are directed between the atoms, so the diamond matrix is extremely hard and brittle. Further there is a large gap between the bonding and antibonding orbitals so electrons cannot jump into the conductance band, so a diamond does not conduct electricity. Model of graphite Graphite is another elemental form of C. However, as you know the lead from a pencil is not the hard clear crystal that diamond is so how is it formed? Here you have sheets of sp2 hybridized C (trigonal planar) . Each plane is one giant molecule but one plane is not bonded to the next so they slip over each other to make an excellent lubricant, or marking utensil. If the C are joined in sp2 hybridized structures, then there are also pi electron bonds forming a molecule continuous above and below the plane. Because this is a delocalized cloud of electrons, graphite, unlike diamond, can conduct electricity. While the alchemist of old tried to convert lead to gold and failed, modern chemist can convert graphite to diamonds all yo need to do is to heat the diamond or 2800oC and put it under 150,000 atm of pressure. In a way this treatment makes sense. You need the heat to break the strong double bonds that compose the graphite matrix, and you need the pressure because graphite has a lower density than diamond and yo need to squeeze the atoms together to get this into the appropriate matrix.

10 Lets now look at Si for a bit. Si is the second most common element in the earth crust ( behind O). The familiar forms of Si that yo observe in nature, however, are not pure elemental forms, but are generally mixtures of Si and O and other compounds. Lets start with SiO2 or silica. You know that CO2 is a gas with the linear structure ::O=C=O:: where the == bond is a combination of an sp hybridized bond and a B bond formed between the 2p orbital of the C and the O. It is logical to expect that SiO2 would be much the same, but it isnt. Because the Si atom is larger than the C atoms (1.2 A instead of .8 A) it is harder to form the B orbital in Si O than in CO because there is less overlap between the p orbital on the adjacent atoms. Because of this Si tend to form tetrahedral sp3 hybridized bonds with 4 oxygens, with each oxygen, in turn, bonding to another Si. The result is a mesh of Si and O molecules Figure 10.26 . This results in a rather hard solid, rather than a gas like CO2. Note that while the empirical formula is SiO2 quartz is actually a network of -Si-O-SiO O -Si-O-SiO O etc. Again skip the following section most years...go Group 8A solids Many rocks, soils and clays are based on closely related silicon compound called silicates. Notice that in silica the O:S ration is 2:1 In Silicates include addition oxygen anions, and hence have O:S ratios >2:1. Since the matric contains negative anions, it also must contain positive cations to balance out the charge so silicates will contain various metal salts. When silica is heated above its melting temp (about 1600oC) and cooled rapidly it forms the an amorphous solid called a glass. The most obvious example of this find of solid made with silica is window glass!. The internal structure of a glass is much more like an extremely viscous liquid than a crystalline solid. (More like a taffy than a sugar crystal). There is some debate as to wether glass actually flows like a liquid over the time scale of 100 years are more. The properties of glass can be varied dramatically by changing the various material that are in the glass melts. Thus we can get colored glasses, hard glasses, glasses that dont change in size when heated (Pyrex). Etc. See table in book. Ceramics Ceramics are another kind of material made from silicates. Your typical everyday ceramic comes from clay (contain silicates) that has been hardened by heating to a high temperature. Ceramics are useful because they are nonmetallic, strong and resistant to heat and chemical damage While they are based on silicates they are really much different than glasses. Glasses can be melted and remelted. Ceramics, on the other hand are not effected much by re-exposure to heat.

11 The difference occurs largely because glasses are homogeneous solution and a ceramic is a heterogenous mixture. It contains minute crystals of silicates suspended in a glassy cement. Clays that form ceramics at the natural product of the weathering of mineral feldspar K2 O Al2O3 6SiO2 or Na 2O Al2O3 6SiO2 One of the prime product of this weathering is kaolite Al2Si2O5(OH)4 This compound forms into very small platelets. These platelets absorb water readily and turn into the slimy mud. However, when the platelets are dried, all the water is released from within the structure and the platelets bond to each other instead of the water. Finally if the clay is fired at high temperature the silicates and cations that are also in the mud fuse into a glass that surround the individual crystals of kaolinite While ceramics have been with out since 3000 BC, they are still a hot area of chemistry lots of high tech chemistry is going on in making ceramics for everything form the heat resistant tiles on the space shuttle, to superconducting wires to engine parts. Semiconductors Since Si has the same electronic configuration as C, and we already know that it has difficulty forming Pi bonds, you should suspect that elemental Si has the same crystalline form as C. Well you are right!! One different however, is that while the matric of C is non-conducting, the energy gap between boning and anti boning is lower in Si so Si will conduct a low level of electron, making it a semiconductor. The conductivity of Si increases with temp as more electrons can jump o the antibonding orbitals(In metals the behavior is just the opposite) The small conductivity of Si can be enhances if it is doped with other elements, that is a small fraction of the atoms are replaced with other atoms, much like the substitutional alloys in metals When Si is doped with elements with more valence electrons than Si we create what are called n-type semiconductors. As might be expected these are better conductors than Si itself. When we use doping elements with less valence electrons we create p-type semiconductors. Surprisingly these are also more conductive than Si itself. A model that helps explain this is to think of the p-type matric as containing holes or gaps that need electrons. Whenever an electron gets popped into a hole, it opens up a different hole, so the current moves by hole displacement The we get interesting interplay of conductivity when we join p-type and n-type semiconductors together. This is what gives rise to diodes, rectifiers, transistors, and computers. Is am skimming badly. How much is this covered by others?

12 Group 8A solids The last atomic solid to look at is the group 8A solids, or solids composed of the inert gases. These solids characterized by the fact that these atoms have no charge, dipole or metallic bonding to hold the atoms together. The only thing that is left is the minimal London force, and even that is minimal because we are dealing with small spherical atoms with a minimum surface area. Very tiny force holding atoms together, so only observed very close to absolute zero. 10.6 Molecular Solids Now lets move from atomic solids to molecular solids. That is instead of atoms at the lattice points, we have molecules at the lattice points. Common molecular solids include water ice and dry ice Also certain forms of sulfur that contain S 8. In these structure we have the typical strong covalent bonds formed between the individual atoms of eh compound, but relatively weak interactions between one molecule and the next. For instance it takes only 6kJ to break the weak dipole interaction that hold a mole of ice together, but it would take 470 kJ to break 1 mole of OH covalent bonds or about 350 kJ to break 1 mole of C-C bonds The forces holding molecule solids together vary from one solid to the next. Some rely only on London dispersion forces, others have dipole interaction, especially prevalent are the hydrogen bonds we talked about earlier. This is a very important interactions in ice (show H-bonded ice structure. 10.7 Ionic Solids Ionic solids are stable, high-melting substances held together by strong electrostatic forces. Talked about some basic structural principles in chapter 8. Now for the details. The structures of many binary ionic solids is just what you would expect for the close packing of spheres. Typically the larger ions (generally the anion) are fit into either a hexagonal or the cubic closed packed systems, and the smaller ion (usually the cation) is packed into the gaps around the anions. This packing minimizes charge repulsions and maximizes charge attractions. There are three kinds of hole in closest packed structure. 1. There is a trigonal hole that exist between 3 spheres in 1 plane 2. There is a tetrahedral hole that exists between 3 spheres when you have 3 in 1 plane and a 4 th making a pyramid 3. Finally there is a octahedral hole that exist when you have one triangle in 1 plane pointed 1 way and a second pointed another Show models of all holes If you think about it you will see that the size order is trigonal < tetrahedral< octahedral

13 Trigonal holes are so small, that they are not used in binary compounds Tetrahedral holes are a bit large and are used in compounds like ZnS radii 70 pm and 180 pm respectively In the Zn S structure the S take a face centered lattice. While this is hard to visualize, if you get a model of a face centered lattice you will find that there are places for 8 tetrahedral holes in this lattice, while it contains a total of 4 S atoms. Since S is -2 and Zn is +2, to have electro neutrality there must be an equal number of Zn and S ions, so the Zn can only occupy 4 of the 8 potential hole positions Octahedral holes are used to position Na in NaCl crystals Here the Cl are located in a closest packed cubic array and the Na are in the octahedral holes (Cl 181 pm, Na 95 pm) Again you would have to study the model to see this easily, but close packed cubic array gives a face centered lattice, in a face centered lattice contains 4 atoms and 4 octahedral holes so all of the octahedral hole can be occupied by Na to have an electroneutral array.

Summary of solids Review table 10.7 10.8 Vapor pressure and Changes of State We have now looked at the three state of matter. Lets worry a bit more about how you change from one state to the next. If we put an open contain of most liquids out in the air we know the liquid will vaporize or evaporate. We can tell this in two ways. Either we may be able to smell the vapor, or we can measure how the volume of the liquid decreases Vaporization is an endothermic process because energy is required to break the attractive forces that hole the liquid together. We make this into a formal property called the heat of vaporization or enthalpy of vaporization )H vap This is the heat required to vaporize 1 mole of liquid at 1 atm. This heat of vaporization has a very practical significance. Why do you sweat? Just because my tests are tough, or to try to cool off? Why are lakes and ocean cooler than land? Etc. Vapor Pressure We were just talking about liquid in an open container. What about liquid in a closed container? If you watch the liquid leaving you will see the liquid level decrease at first then level off. What is happening? (Rate of evaporation constant, rate of condensation starts at 0 because nothing in gas, but then increases until matches rate of evaporation. Figure 10.37 Reach equilibrium Evaporating and condensing at the same rate. So individual molecules are going into the gas and returning to liquid but net no charge. Because two forces are balanced against each other.

14 The pressure of the vapor when it is at equilibrium with the liquid is called teh equilibrium vapor pressure or the vapor pressure of the liquid. Vapor pressure may be measured easily with a slight modification of our standard mercury barometer. Figure 10.38 - Skipped this in 1998. You should remember that if you fill a tube with mercury (Hg) and turn it upside down, you can the vacuum will hold a column of mercury 760 mm high. This is how we defined out atomospheric pressure as 760 torr. Here we have P atmosphere = P hg column Now all we will do is inject a little of teh liquid we wish to measure into the mercury. Since mercury is very dens teh liquids rises to the top, and vaporizes until the liquids and gas are in equilibrium, and this increases volume of the second gas lowers the height of the Hg column. Now we have Patm = P hg column + P vapor Rearranging this last equation we have Pvapor = P atm - P hg column when liquid is in Thus our Pvapor is the difference in the Hg level before we added the liquid (P atm) the Hg level after we added the liquid (P hg column when liquid is added) Return to useful info a Volatile liquid is a liquid with a high vapor pressure. In liquids with large intermolecular forces have low vapor pressures because it takes more energy to remove a molecule from the liquid. If liquids were only held together by London dispersion forces yo would expect large molecules to have lower vapor pressure than smaller molecules because they have smaller London interaction. If this is so, then why does water with a relatively time MW have a relatively low vapor pressure? (Polar H bonds, polarity If we measure vapor pressure as a function of temperature we see that VP increases significantly with temperature see for example figure 10.40. Why would this be? Need a certain level of Kinetic Energy to break out of liquid. At higher Temp have higher KE distribution, so more molecules are over the edge see figure 10.39 Notice that the plots Is drew fro Vp vs temp are curved. If we plot ln(P vap) vs 1/T get straight line Back to plot 10.40) This is actually a very handy plot because or lets us determine the )H of vaporization. It can be shown (meaning Is wont do it here, take my word for it) that

ln( Pvap ) =

Hvap 1 +C R T

So of we plot ln(P vap) is 1/T, the slope = -)H/R Lets try an example. From figure 10.40 we find the vp of ethanol at 30oC is about 100 torr and at 60oC is about 360 torr. Converting oC to K we have and getting 1/T

15 30 + 273.15= 303.15 = .0033 60+273.15 = 333.15 = .0030 Taking ln (P vap) ln(100 torr) = 4.61 ln(360 torr) = 5.89 This give us a line in this direction \ Note that our T1 temp is at lower left and our T2 temp is at upper right What is slope of line ? Change in y/change in X = (4.61-5.89)/ (.0033-.0030) = -4,270 -4,270 =- )H/R = X/8.3145 J/K )H = 35.5 kJ/mol This is about 3/4 the value for the heat of vaporization of water (43 kJ/mol) Note that we can also turn the problem around. If Is give you a )H of vaporization and a vapor pressure at a single temperature, you can calculate for me the vapor pressure at a different temperature SEE EXERCISE 10.6 do this kind of example see problems 73-76? Solids, like liquids also have a vapor pressure Bring dry ice or mothballs Dry ice or mothballs are a prime examples. When a solid transforms directly to a gas without going through a liquid state we call this sublimation. Other example of sublimation are dry ice - CO2 and water ice. (Ever notice how snow can disappear without melting?) Changes of state Changes of state occur when you move from one form (s, l, g) to another Lets study this process. First. Help me figure out what will happen if Is take a block of ice out of a -20oC freezer ant let it warm to RT. Temp rises from -20 to o then holds until all ice melted then rises again to 100 then holds at 100 until all liquid turned to solid then rises agin until get hot enough that can break the covalent bonds between H and O and is no longer water. (Note: solid-liquid-gas changes in physical state due to changes in interaction between molecules. H2O gas to H2 and O2 gas is a chemical change due to changes in bonding within the molecule - NOT a change of state) This is called a heating curve. Figure 10.42 The temp where solid turned to liquid was the melting point the enthalpy change that occurs as the solid changed to liquid is the heat of fusion or enthalpy of fusion or )Hfus The MP and )Hfus for several familiar compounds is given in Table 10.9 Now what we just did was simple, you all understood it because it is something you have dealt with often. MP is the temp at which a solid melts (or liquid solidifies) and the BP is the temp at which a liquid vaporizes (or a vapor condenses)

16 Notice however that these definitions are a bit inexact. You can superheat liquids (et them above the BP without boiling) or supercool a liquid (cool it below its MP without forming solid). Indeed, is you get very picky you can remember that all liquids have some vapor pressure at any temp, so technically they are vaporizing at a temp well below their BP. What we want is a much more exact definition of MP and BP. They Key to this better def comes from observing Vapor pressure. Lets look at the VP of water and ice just above and below the MP, 0 Figure 10.43 Notice that the VP of solid is lower <0 and the VP of the liquid is lower >0. We will define the normal melting point as the temp at which the solid and the liquid have the same vapor pressure under conditions where the total pressure i.e. 1 atm. Also note that this is a special point where solid and liquid can coexist. Lets see if this makes sense. Set up as in 10.44 if Temp < this point, then solid has lower vp, and liquid will move or solid and freeze. If Temp > this point, then liquid has lower VP and solid will move to liquid and melt if Temp = this point, then in equilibrium and liquid and solid can coexist. Now lets continue to increase the temperature, what happens to the vapor pressure? (It continues to rise) What happens when the liquids vapor pressure equals the atomospheric vapor pressure? (Liquid start turning into gas and gas bubbles form because internal pressure inside bubble equals external atmospheric pressure. In simpler terms- it begins to boil!) In similar manner will define The normal boiling point as the temp at which the vapor pressure of the liquid is exactly equal to 1 atm. This def also makes sense. Bubbles cant form in liquid when temp makes VP < 1 atm, but will form when Vp = 1 ATM 10.9 Phase Diagrams We have been talking about changes in physical state or phase; lets look at a way to plot these changes of state in a way that is useful. A phase diagram is a convenient way of representing the phases of a substance as a function of temperature and pressure. Also note that a phase diagram represents what occurs in a closed system. That is, nothing gets in or out of the system, system at equilibrium Lets start with a phase diagram for a substance you are familiar with water. Figure 10.47 or 10.48 Example 1 -1 atm of pressure. Fill cylinder with ice at low temp. Hold pressure steady at 1 atm. Note at low temps

17 is solid, at this temps is liquid at even higher is gas. Just what we expected as said earlier. Note that these are all clean transition. There are never any gas bubbles or liquid droplets it is either 1 form or the other. Example 2 -Now try at a lower pressure (below tripl point) Note here go from solid to gas with no liquid - sublimation Example 3- Now try at pressure = 4.58 torr. Hit an interesting point, the triple point. This is one place where the cylinder can contain s, l, and g it is at 0.01oC (273.16K) 4.58 torr This diagram says that this is the only place where this can occur Example 4. Lets try a couple at the l-G interface at 1 atm and below Note how our BP varies with pressure. What would be a practical application of this? BP of water around here is 97o C If Go to Bolder Co. (5,430 ft) in the mountain, pressure is 610, BP is 94 If go to Leadville CO (10,150) Pre = 510, BP = 89 Practical application Boiling you vegies, dont get cooked. Stay crisp! Example 5. Note This line has an end! Doesnt continue on forever. Here get a transition from water to gas, but not clean liquid goes to Gas going through an intermediate fluid that doesnt act like a gas or a liquid. The temp above which vapor cannot be liquified, no mater what the pressure is called the critical temp The pressure at which you can get liquefaction at the critical temp is called the critical pressure. Combined we called this point the critical point The critical pont for water is 374oC, 218 atm Example 6 vary pressure at low temp - may explain why you can skate on ice. At high pressure changed to liquid, gives lubrication, you skate. (May not be only explanation). NOTE: this behavior is UNIQUE to water. Most other substances have a + slope here instead of - so doesnt happen (will show a more typical solid in a minute) Why would this be so? One of the unique properties do water is that the solid is LESS dense that the liquid. Makes sense, if apply pressure, want to go into a smaller space. Is liquid is more dense (more matter in a smaller space) then pressure should favor liquid state Phase diagram for CO2 For contrast lets look at the phase diagram for CO2 Figure 10.52 This has a more normal + slope at 1 atm transition from solid to gas occurs at -78, so what is the temp of something you just pulled out of dry ice? (-78) Triple point 5.1 atm, -56.6 oC, critical point at 72.8 atm 31oC Many fire extinguishers contain CO2. If they contain liquid CO2 what would the internal pressure have to be?(close to 70 atm)

18 When release liquid goes to gas, cools off fast. The white fog is actually water NOT CO2! CO2 is also heavier than air so settles (Should CO2 be heavier than air? How can tell (Air is mostly N2; N2 has MW of 28, CO2 has a MW of 12+16+16= 44) Another practical application. We just talked about the critical point. When you get a fluid up into this region between liquid and gas you have what is called a super-critical fluid. This may sound like some exotic came talk, but it has very day-to-day applications. How do you decaffeinate coffee? One way is to extract with thing like chloroform, or CH2Cl2 (dichloromethane). Not very appetizing. Another way is with supercritical CO2! In fact this is how the bulk of decaffeinated coffee is produced. Put it in the CO2 at high pressure and RT and the caffeine leaches out of the coffee bean. Drop the pressure and , boil off the CO2 and you bean is decaffeinated! What do you do with the caffeine you have left? You sell it to the people making soft-drinks!

O N
O N CH3

CH3 N N

Caffeine