Intermolecular Forces and Liquids. Kinetic Molecular Theory According to the Kinetic Molecular...
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Transcript of Intermolecular Forces and Liquids. Kinetic Molecular Theory According to the Kinetic Molecular...
Intermolecular Forces and Liquids
Intermolecular Forces and Liquids
Kinetic Molecular Theory
• According to the Kinetic Molecular Theory, ALL particles of matter are in constant motion.
• This theory helps explain the behavior of solids, liquids, and gases.
Behavior of gases
• Particles in a gas are never at rest.
• Gaseous atoms travel in a straight line until it collides with either another atom or the wall of the container.
• The constant motion of gas particles allow it to fill a container of any shape or size.
Behavior of liquids
• Particles in a liquid are more closely packed than the particles in a gas.
• Therefore, attractions between the particles in a liquid do affect the movement of the particles.– It slows them down – less kinetic energy
• A liquid takes the shape of its container because particles can flow to new locations.
• The volume is constant because forces of attraction keep the particles close together.
Behavior of solids
• Solids have a definite volume and shape because their particles vibrate around fixed locations.
• Strong attractions restrict motion and keep each atom in a fixed location relative to its neighbors.
• Atoms vibrate around its location but it does not exchange places with neighboring atoms.
Phase changes
• The reversible physical change that occurs when a substance changes from one state of matter to another.
Forces that hold atoms and molecules together
• Ionic Bond: due to electrostatic attraction between opposite charges (ionic compounds).
• Covalent Bond: due to combining of atomic orbitals when electrons are shared.
• Intermolecular Forces: due to electrostatic attraction between opposite charges (ionic and covalent compounds).
Summary of Intermolecular Forces
Van der Waals intermolecular forces:• Ion-dipole forces• Dipole-dipole forces
– Special dipole-dipole force: hydrogen bonds• Forces involving nonpolar molecules: induced
forces• Dispersion or London forces.
Two factors affect the strength of ion or dipole force (Coulomb’s law)
• Magnitude of charge• Distance
Generally – order of strength
Strongest: Ionic Bonds Ion-dipole bonds
Hydrogen Bonding Dipole forces Induced dipole
Weakest: Dispersion forcesReflects in properties
Comparing Properties
Melting Point, Boiling Point, Heat of Fusion, Heat of Vaporization, Surface tension, viscosity - - - all go up as strength of IMF increases
Vapor pressure – goes down as strength of IMF increases (higher IMF makes evaporation less likely and less gas molecules mean lower vapor pressure)
Ion-Ion Forcesfor comparison of
magnitude
Na+—Cl- in saltThese are the
strongest forces. Lead to solids with
high melting temperatures.
NaCl, mp = 800 oCMgO, mp = 2800 oC
Attraction Between Ions and Permanent Dipoles
Attraction between ions and dipole depends on ion charge and ion-dipole distance.
Dipole-Dipole ForcesDipole-Dipole Forces
Dipole-dipole forces bind molecules having permanent dipoles to one
another.
Dipole moment
• Polar molecules or dipoles have positive and negative side.
• A measure for the polarity is the dipole moment (p. 376).
• Dipole moment is given in Debye (D).
Hydrogen BondingHydrogen BondingA special form of dipole-dipole attraction, which enhances dipole-dipole attractions.
H-bonding occurs when X and Y are N, O, or F
Watch out!
Hydrogen must be connected to F, O, or N. Not all hydrocarbons with these atoms present contain hydrogen bonding.
Example:Dimethyl ether: CH3 – O – CH3
does NOT have hydrogen bonding.Methanol: CH3OH
does have hydrogen bonding.
H-Bonding Between Methanol and WaterH-Bonding Between Methanol and Water
H-bondH-bondH-bondH-bond
Hydrogen Bonding in H2O
Hydrogen Bonding in H2OH-bonding is
especially strong in water because
• the O—H bond is very polar
• there are 2 lone pairs on the O atom
Accounts for many of water’s unique properties.
Hydrogen Bonding in H2O
Hydrogen Bonding in H2O Ice has open
lattice-like structure.
Ice density is < liquid.
And so solid floats on water.
A consequence of
hydrogen bonding
H-bonding leads to abnormally high specific heat capacity of water (4.184 J/g•K)
This is the reason water is used to put out fires, it is the reason lakes/oceans control climate, and is the reason thunderstorms release huge energy.
DNA Base-Pairing through H-BondsDNA Base-Pairing through H-Bonds
Boiling point of water
• Water has a very high boiling point compared to other simple hydrogen containing compounds, such as CH4, H2S, and even NH3 and HF (which exhibit H-bonding as well, but less “extreme” as H2O
Boiling Points of Simple Hydrogen-
Containing Compounds
FORCES INVOLVING INDUCED DIPOLESFORCES INVOLVING INDUCED DIPOLES
How can non-polar molecules such as O2 and I2 dissolve in water?
The water dipole INDUCES a dipole in the O2 electric cloud.
Dipole-induced dipoleDipole-induced dipole
FORCES INVOLVING INDUCED DIPOLES
FORCES INVOLVING INDUCED DIPOLES
Solubility increases with the mass of the gas
Process of inducing a dipole is polarizationDegree to which electron cloud of an atom or molecule can be distorted in its polarizability.
Dispersion forces
• Induced dipole – induced dipole• Between 2 non-polar molecules.• Caused by the movement of the electron
cloud.• The more electrons (higher molar mass) the
stronger the force (higher MP and BP).
FORCES INVOLVING INDUCED DIPOLES
FORCES INVOLVING INDUCED DIPOLES
Formation of a dipole in two nonpolar I2 molecules.
Induced dipole-induced dipole(dispersion)
Induced dipole-induced dipole(dispersion)
FORCES INVOLVING INDUCED DIPOLES
FORCES INVOLVING INDUCED DIPOLES
The induced forces between I2 molecules are
very weak, so solid I2 sublimes (goes from a solid to gaseous molecules).
FORCES INVOLVING INDUCED DIPOLES
FORCES INVOLVING INDUCED DIPOLES
The magnitude of the induced dipole depends on the tendency to be distorted.
Higher molar mass = stronger forces Molecule Boiling Point (oC) CH4 (methane) - 161.5
C2H6 (ethane) - 88.6
C3H8 (propane) - 42.1
C4H10 (butane) - 0.5
Boiling Points of Hydrocarbons
CH4
C2H6
C3H8
C4H10
Note linear relation between bp and molar mass.
LiquidsLiquids In a liquid• Molecules are in
constant motion• There are
appreciable intermolecular forces
• Molecules are close together
• Liquids are almost incompressible
• Liquids do not fill the container
Liquids: Energy and Phase changes
Melting and Freezing
• Melting: add energy to break bonds that keep molecules at fixed position (kinetic energy goes up): endothermic
• Freezing: energy released (kinetic energy goes down) as particles “settle” in fixed positions: exothermic
LIQUID VAPOR
Evaporation: Add energy to break IM bonds
Condensation: Remove energy to form IM bonds
Evaporation and condensation
To evaporate, molecules must have sufficient energy to break IM forces. This breaking requires energy, so the process of evaporation is endothermic.
Evaporation
Condensation
• When a gas or vapor condensates, the kinetic energy of molecules gets lower, while IM forces get stronger. Energy is released: this process is exothermic.
Distribution of Energy in a Liquid
.
0
Nu
mb
er o
f m
olec
ule
s
Molecular energy
minimum energy neededto break IM forces and evaporate
higher Tlower T
At higher T a much larger number of molecules has high enough energy to break IM forces and move from liquid to vapor state.
High E molecules carry away E. You cool down when sweating or after swimming.
When molecules of liquid are in the vapor state, they exert a VAPOR PRESSURE.
EQUILIBRIUM VAPOR PRESSURE is the pressure exerted by a vapor over a liquid in a closed container when the rate of evaporation = the rate of condensation.
Liquid in flask evaporates and exerts pressure on manometer.
Measuring Equilibrium Vapor Pressure
Measuring Equilibrium Vapor Pressure
HEAT OF VAPORIZATION
HEAT OF VAPORIZATION is the heat required (at constant P) to vaporize the liquid.
Compd. ∆vapH (kJ/mol) IM Force
H2O 40.7 (100 oC) H-bonds
SO2 26.8 (-47 oC) dipole
Xe 12.6 (-107 oC) induced dipole
Heat of vaporization
• How much heat is needed to vaporize 6.51 mL of water? (ΔvapH = 40.7 kJ/mol)
• Density of water = 1.0 g/mL, so 6.51 mL = 6.51 g• 6.51 g/18.02 g/mol = 0.361 mol H2O• 0.361 x 40.7 = 14.7 kJ
Boiling Liquids
Liquid boils when its vapor pressure equals atmospheric pressure.
Liquid boils when its vapor pressure equals atmospheric pressure.
Then bubbles of vapor form within the liquid.
Then bubbles of vapor form within the liquid.
Boiling point
Boiling occurs when a liquid turns to a gas inside the liquid◦bubbles are produced
Liquid boils when its Vapor Pressure = Atmospheric Pressure◦Normal boiling point
Larger IMF = lower vapor pressure = high BPWeaker IMF = high vapor pressure = lower BP
Molecules at surface behave differently than those in the interior.
Molecules at surface experience net INWARD force of attraction. This leads to SURFACE TENSION — the energy required to break the surface.
Surface Tension
Surface Tension
Surface Tension also leads to spherical liquid droplets
Surfactants• Surface tension can be decreased by adding
surfactants (soap, detergents).• They interfere with hydrogen bonding.
Capillary action
IMF also lead to capillary action and to the existence of a meniscus for a water column.
This is caused by ADHESIVE
FORCES between water and glass
Capillary Action
Movement of water up a piece of paper depends on H-bonds between H2O and the OH groups of the cellulose in the paper.
Viscosity
• Resistance to flow – • Goes up as IMF increases• Also goes up as length of
hydrocarbon chain increases as molecules get tangled up and don’t flow easily
Phase diagram
• We use these diagrams to relate the process that occur when a substance changes from one phase to another.
• Substances are in the following states when in certain locations on the diagram:– Solid – left side of diagram– Liquid – middle of diagram– Gas/Vapor – right side of diagram
• When either the temp or pressure is changed, you can identify the process that is taking place and identify the phase change.– Ex (from diagram on last slide) – At 1 atm if you
increase the temperature from 90oC to 200oC, the process you are undergoing is vaporization or boiling (liquid to gas).
Triple point• The change of state occurs right on the
equilibrium line.• Triple point identifies the conditions
when you have all 3 states in dynamic equilibrium with one another.
Normal MP and BP
• Tm normal melting point–The point at 1 atm or 101.3 kPa
when solid turns to liquid.• Tb normal boiling point
–The point at 1 atm or 101.3 kPa when a liquid turns to a vapor
Critical point
• Critical point – you are no longer able to distinguish between gas and liquid phases past this point.
CO2 Phase diagram