Properties of Liquids and Solids Chapter 11, p.

467-519


The physical state of a substance depends largely on a balance between the kinetic energy (temperature) of particles and the attractive forces between the molecules (intermolecular force)

Assignment Chapter 10.

Assignment:
over the presentation. Read chapter 10 if you need clarification. Understand how structure and intermolecular forces can be used to explain several physical properties such as vapour pressure, boiling point, etc. Make sure you understand the phase diagram for carbon dioxide and carbon on p.496-499. Review Questions; Zumndahl p. 500-506 # 35, 37, 38, 41, 67, 68, 87, 88, 89, 90, 91, 93
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Phases of Matter: Solid, Liquid and Gas

Intermolecular Forces

Intermolecular Forces (review):



London Dispersion Force

- due to movement of electrons causing momentary dipoles. - more electrons, Larger molar mass ==> greater LDF

- present in any atom/molecule



Dipole-dipole Force
- polar molecules, dipole bonds ==> electrostatic attraction.

Hydrogen Bonding
- large dipole bonds => O-H, N-H, H-F

Comparing particles of similar sizes:

LDF < D-D Force < H bond

Ion Dipole forces: forces that exist between an ion and a polar molecule.
This attraction between a polar covalent compound and an ion is responsible for the something like sodium chloride dissolving in water.

Why does a gas condense into a liquid?



a gas condenses because the kinetic energy is lowered to such a point that the intermolecular force becomes more significant than the KE (movement keeping them apart) in bringing particles close together causing the gas to turn into a liquid.

Explain in terms of intermolecular forces, why water boils at 100RC and ethanol boils at 78oC?
Water molecules are held together by hydrogen bonding. Ethanol molecules are also held together by hydrogen bonding. But ethanol molecules are larger (CH3-CH2-OH) causing a disruption to the hydrogen bonding, thus reducing the intermolecular attraction. Since ethanol molecules have lower intermolecular attraction, then a lower temperature can break the intermolecular forces between molecules causing them to separate, thus boiling at a lower temperature.

Explain the trends found in the graphs showing the relationship between molar mass and boiling points:

The red line.



In the red line, water has a large b.p. because of the large polarity of the O-H bond causing the molecules to be held together with a strong intermolecular force (hydrogen bond). The other molecules have lower dipole and the intermolecular force is the dipole-dipole force. The boiling point increases from H2S to H2Te because of the increase in molar mass, thus increasing the London dispersion force holding the H2Te molecules together giving a larger b.p.

The black line.



All molecules are non-polar so the intermolecular force holding the molecules together is London Dispersion Force. The size of the molecule (number of electrons) determines the magnitude of the London Dispersion Force. If you have more electrons, there is a greater polarizability of the electrons leading to greater intermolecular force (allows for greater momentary induced dipole). You observe a larger b.p. for larger molecules due to larger intermolecular force holding the molecules together.

Why can this bug walk on water?

This is due to the surface tension of water. The hydrogen bonding holds molecules of water together. This attraction is so strong that the mass of the bug cannot break the attractive forces between water molecules thus preventing the bug from sinking into the water

Why a liquid such as water changes into gas (evaporates) even if the solution is below the boiling point?
Particles are always moving. Some particles are moving fast enough to escape the intermolecular attraction that holds the particles in the liquid phase (see diagram in next slide). As molecules evaporate, the liquid loses particles into the gas phase (and Kinetic Energy). The liquid cools. This is the reason sweat is used as a cooling mechanism. Factors that control the rate of evaporation
1. surface area of the liquid 2. temperature 3. strength of intermolecular forces

Graph showing the distribution of particles at two different temperatures and the fraction of particles having enough KE to escape from a liquid to a gas phase:

Hydrogen bonding is responsible for the structure solid water as a snow flake or for a organized structure in ice. Ice floats because its organized structure takes up more volume (so lower density) than water thus causing ice to float in water.

Vapour Pressure

Vapour Pressure

Vapour Pressure


 

A Liquid is placed in an empty closed vessel at a particular Temperature. Some liquid evaporates. The gas exerts a pressure on the walls of the vessel. This pressure is referred to as the Vapour pressure of the liquid.

Liquid with high vapour pressure..



provides some indication about the intermolecular force holding each the molecules together. If the intermolecular force holding the molecules is low, then more liquid would change into a gas easily with an increase in T. So the vapour pressure of this liquid would be high (due to more gas particles). These liquids are said to be volatile liquids.

Explain the differences in vapour pressures for each liquid in terms of intermolecular forces.

Vapour Pressure
e.g. b.p. of water in Vancouver is 100oC b.p. of water on top of Mt. Everest is 70oC

Hmm

Why does water have different

boiling points at different places?

Boiling==>

vapour pressure of liquid equals atmospheric pressure

 

When a liquid boils, bubbles are formed. These bubbles are really filled with water vapour. The only way vapour can form is when the vapour pressure of the liquid equals the atmospheric pressure. Therefore, water boils at a lower temperature when the atmospheric pressure is lower (top of Mt. Everest). Normal boiling point is standardised at 1 atm (sea level, Vancouver), or this is temperature at which a vapour pressure equals one atmosphere. Note that liquids with high boiling points result from ___strong______intermolecular attraction.

Vapour Pressure relationship with Heat of Vaporization:

Vapour Pressure and enthalpy of vapourization:

Energy changes and Intermolecular attraction (see p. 484-488 Zumndahl) (H vaporization and (H sublimation represent the energy needed to separate molecules from each other. Therefore, these values provide us with a good value to compare the strength of intermolecular attractions. e.g. H2O =+43.9 kJ/mol I2 =+22 kJ/mol Therefore, water has a greater intermolecular attraction than iodine.

Phase Diagrams
How temperature changes as heat is added or removed as time progreasses. This is the usual phase diagram from chem 11.

Temperature changes during phase change

In a heating curve (constant P)  At the flat sections, the average Kinetic Energy of the particles are not changing,  so the energy added to the system is being used to increase the Potential Energy (separation, breaking intermolecular bonds) of the particles.

The bump on the cooling curve is due to the fact that the particles in the liquid phase are still disorganised and do not form the crystal structure found in a solid. Therefore, the system still cools (SUPERCOOLING). Crystallization needs a seed to get crystal growth started. When solid crystals start forming, energy is used to change phase. Temperature changes back to the correct freezing temperature.

Temperature changes during phase change

How energy Changes during phase change



Since Enthalpy is defined as the total Kinetic and Potential Energy at constant temperature and pressure, we can talk about the energy changes during phase changes. (Hfusion molar energy of fusion (melting)- Energy required to melt one mole of a substance at constant temperature. (Hvaporatization- molar energy of vaporisation (vapour)- Energy required to vaporize one mole of a substance at constant temperature. (Hsublimation- molar energy of sublimation All of these enthalpy changes will be positive since there is an increase in P.E.

Phase Diagrams
Pressure-Temperature Diagrams

Presure-Temperature Phase Diagram

Notes on the phase diagram:



 

 

Line: represent the when phase change occurs at a particular pressure and temperature. Represents equilibrium in phase change e.g. s < ==>l, l < == >g, or s < == g. Critical Point: Highest temperature at which a liquid can exist.... - beyond this temperature, the KE is so large that the substance only exist in the gas phase. - No liquid phase can exist at this point (374oC and 218 atm for water) Triple point: All three phases are at equilibrium. - All known substances except helium have a characteristic Triple point.

Difference between the phase diagram of water and other substances (e.g. CO2):
-the solid-liquid equilibrium line leans backwards

-Following the arrow in the phase diagram of water - Pressure increase with a constant temperature.


As pressure increases, density also increases. Then water vapour freezes into ice. As pressure increases, ice turns into WATER!! So water is denser than ice, so ice floats in water.

-Why can you ICE skate, but cannot DRY Ice (CO2) skate well.. follow the arrow.


As Ice is compressed (increase in pressure) by the blades of a skate, ICE turns into water. This thin film of water acts as a lubricant, allowing the blade to slide So you can skate on ICE.

In dry ice, or solid carbon dioxide.



 

Following the arrowAs the blade of your skate compresses the dry ice, it remains as a solid. There is no liquid CO2 to act as a lubricant, and you do not glide very well. So you can not skate on dry ice. Note that you can never get liquid CO2 at normal conditions, but you can at very high pressure. I guess CO2 is not dry after all.

Using the phase diagram, explain how food is freeze dried (drying without boiling the water away or commonly known as cooking) from the food.


1. Food is cooled and the water in it freezes. 2. Then the food is placed in a container and the pressure lowered. Ice in the food sublimes. 3. Pressure and temperature is returned to normal conditions. The food is dehydrated.

1 2

The Solid State

Variations in bond type lead to different structures in solids. In this section we will discuss four different types of structure and the properties of such structures. 1. Covalent network 2. Molecular 3. Ionic 4. Metallic

Covalent-network solids: Giant atomic structures; carbon

. E.g. Diamond and graphite.

Covalent network: Diamond



structures are made of carbon atoms covalently bonded together in a continuous network. The diamond structure is based upon the tetrahedral unit, graphite on a layered structure. All the covalent bonds in these structures are very strong leading to them having high melting and boiling points and them being hard solids.

Covalent network: Graphite

 

conduction

conduction 

1) conducts electricity only in one plane. each carbon is only bonded to three others. This leaves one of the outer electrons "free". Each carbon atom has one such "free" electron and these are spread out over each layer (delocalised). This leads to a "sea" of electrons similar to that in the metallic structure and graphite's ability to conduct electricity along the layers. Since the electrons cannot move between layers there is no conduction in the vertical plane.

2)

It can be used as a lubricant. Weak dispersion forces hold the layers in graphite together represented by the dotted lines on the diagram. As a result they can slide over one another. Thus making graphite a good lubricant.

Covalent Network: Quartz

SiO2 molecules are covalently bonded in a tetrahedral network. Very hard and has high b.p.

Covalent network: Silicon carbide, SiC



 

Covalently bonded network of SiC molecules. Very hard Most made artificially, rare in nature. Used in sandpaper, made into ceramics (used in car brakes).

Molecular Structures: Iodine I2

 

 

Iodine molecules are made up of iodine atoms bonded together producing I2. They attract each other by London London Dispersion force (it is a nonpolar compound) Relatively weak intermolecular force that depends on # of electrons. Low M.P. (113 o) Often confused w/ Covalent network. I2 and other I2 are held together by London Dispersion forces, while C and C in diamond is held together by covalent bonds.

Molecular Structure, I2


Form lattice structure similar to NaCl, but has much lower m.p. due to weaker intermolecular force. Non-conductor as electrons are not free to move since they are involved in the bonding between I-I.

Ionic Structure, NaCl



  

Ions held together by string electrostatic attraction (ionic bond) High m.p. Non-conductor as a solid. Can conduct electricity if molten or dissolved in water as ions are capable of exchanging charges.

Metallic Structure
 

Made up of metal atoms only. Bonding is due to attraction of metal nuclei to the delocalized electrons throughout the solid. The loosely held electrons gives metals characteristic properties such as malleability, ductility, and good conduction of heat and electricity.

Summary

Assignment Chapter 10.

Assignment:
over the presentation. Read chapter 10 if you need clarification. Understand how structure and intermolecular forces can be used to explain several physical properties such as vapour pressure, boiling point, etc. Make sure you understand the phase diagram for carbon dioxide and carbon on p.496-499. Review Questions; Zumndahl p. 500-506 # 35, 37, 38, 41, 67, 68, 87, 88, 89, 90, 91, 93
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