Chapter 16.10 and 16.11: PHASE CHANGES VAPOR PRESSURE Figure 16.44: Behavior of a liquid in a closed container.

Initially mostly evaporation occurs, but eventually rate of evaporation equals rate of condensation At equilibrium: if NO other gas present than liquids vapor, P = Vapor Pressure of liquid = Pvap VP is INDEPENDENT of container size - as long as theres SOME liquid! Measuring vapor pressure of a liquid using a simple barometer. Figure 16.46: Ordinarily the height of Hg in the column is a measure of atmospheric pressure But if some liquid is trapped in the top of a second mercury barometer, it generates a VP which then forces some Hg down the tube. The two barometers can be compared to see the VP of the liquid in the second barometer. Why vapor pressure rises steeply with increasing temperature: Figure 16.47: Attractive forces tend to discourage evaporation and encourage condensation. Molecules must break free of the bulk liquid to evaporate! As T increases more of them have enough KE to do so! Figure 16.48: Vapor pressure of water, ethanol, and diethyl ether as a function of temperature. The STRONGER the IM forces ..... the LOWER the vapor pressure of the gas! BOILING: When its VP = Ambient P, a liquid BOILS. Normal boiling point: Temperature when VP = exactly 1 atm It can be shown that: ln (Pvap) = - (Hvap/RT) + C y = mx + c

(C is a constant for a given liquid.)

The steeper the slope, the larger the intermolecular forces

Clausis-Clapeyron equation: Predicting how vapor pressure changes with temperature: Don't forget! As T increases, VP will increase. Values can be tabulated e.g.Table 16.7

SOLIDS also have a vapor pressure.Figure 16.49: Some solids (e.g. I2 , CO2) sublime at 1atm. Can be used to purify some substances (if one sublimes more readily at a lower temp) Ice has only a tiny VP but its enough to enable the defrost cycle to work! MELTING: Normal melting point: Temperature when VP (solid) = VP (liquid) and Ptotal = 1atm Stronger IM forces will mean the VP of solid and liquid rise more slowly so MP will be higher Figure 16.51: The vapor pressures of solid and liquid water as a function of temperature SUPERCOOLING: Cooling a liquid so fast it does not get change to freeze. SUPERHEATING: Heat a liquid so fast it does not get chance to boil BOTH given any trigger (dust, slight vibration) will suddenly finish freezing (or boiling). This can be quite dangerous (esp. for boiling)

Enthalpies of Physical Processes CHANGES OF STATE: Melting(Fusion) Boiling (Vaporization) Sublimation

Freezing Condensing Deposition

Why not E? These processes occur at constant pressure so we quote H not E. NOTE: H for a given process usually varies only slightly with temperature. e.g., Hvap (enthalpy change of vaporization) of water at 100C and 25 C are similar. H values of physical processes UNITS: kJ/mol (check your units!) ALL VALUES WILL BE SUPPLIED FOR EXAMS ALL VALUES GIVEN ARE POSITIVE: for the ENDOTHERMIC processes. H for an EXOTHERMIC process is just the negative of the reverse process. e.g., Hcondensation = - Hvaporization Heating / Cooling Curves Must break the calculation into steps of changes of state, temperature: (see below) During change of state, TEMPERATURE is CONSTANT SLOPES of temperature vs. heat supplied varies with the heat capacities of each state of matter.. The energy required to melt a substance is much less than that required to vaporize it. Why?? Using H values For heating a substance use one of the heat capacity/specific heat equations, e.g. : q = mCsT where Cs is in J/gC or J/gK* q = nCmT where Cs is in J/molC or J/molK* For a phase change use: q = mH where Hvap or Hfus is in J/g* q = nH where Hvap or Hfus is in J/mol* *Remember a change of 1C and 1K are identical. Compare this generic diagram to Figure 16.50: The heating curve for water.

KEY POINTS: 1. NO CHANGE IN TEMPERATURE OCCURS during a PHASE CHANGE. All heat goes into giving particles the energy to move about more and separate from each other. 2. AMOUNT OF HEAT NEEDED TO MELT A SOLID IS USUALLY LESS THAN THAT NEEDED TO VAPORIZE LIQUID. In a gas the particles spend most of their time far apart so the IM forces must be fully overcome. Example. A swimming pool containing 10,000L of water has frozen solid at -5 C. (Assume its one of those above ground ones). A 40kW heater (40kJ/s) is to be used to melt the ice and heat the pool to 20 C. How long does the heater have to run? (density of ice is 0.917 g/mL, specific heat of ice is 2.03J/g C, Hvap ice is 6.01kJ/mol and specific heat of water is 4.184J/g C)

Example 2: H fus of benzene is 10.59 kJ/mol. I have 47g of liquid benzene at its melting point, 278.6K. If I remove 2kJ of heat energy from this sample, what is the final temperature?

PHASE DIAGRAMS: Shows at which temperatures and pressures each phase can exist. NOTE: PHASE DIAGRAMS are constructed for ISOLATED systems. A puddle, or an ice cube in a freezer, etc., is NOT an isolated system A mix of ice and water in a Thermos type flask is APPROXIMATING an isolated system I will make some comments about each diagram; you may want to add these to the reproduced figures below. Figure 16.55: Phase diagram for H2O

Figure 16.55: Phase diagram for CO2

Table 16.9 shows why you cant make a decent cup of tea up a mountain.