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B. London forces
-Form when an instantaneous dipole induces a dipole
Comparing IMFA
A. Comparable molecular weights and shapes
Dispersion forces are approximately equal
Look for dipole–dipole attractions or H-bonding
-Greater polarity, stronger IMFA
-H-bonding has strongest interactions
B. Wide difference in molecular weights and no H-
bonding
Dispersion forces dominate
-Higher MW, stronger IMFA
C. Vapor pressure
Pressure exerted by its vapor when the liquid and
vapor states are in dynamic equilibrium
Dynamic Equilibrium- State wherein the rates of the
forward and backward processes are the same
Properties of Liquids
A. Viscosity
Resistance of a liquid to flow
Stronger the intermolecular forces of attraction, more
viscous the liquid
Presence of structural features that cause molecules
to become entangled increases viscosity Substances with high vapor pressure evaporate more
Increasing temperature decreases viscosity quickly than substances with low vapor pressure
-Stronger the IFA, the lower the vapor pressure
Which of the following pairs of substances will be more
Liquids that readily evaporate are said to be volatile
viscous?
Vapor pressure increases with increasing temperature
Br2 or N2 = Br2 HCl or HBr= HBr
CO2 or HCl= HCl Which of the following pairs of substances will have the
B. Surface tension higher vapor pressure?
Energy required to increase the surface area of a CH4 or H2O = CH4 HCl or HF = HF
liquid by a unit amount Br2 or N2 = N2
Due to imbalance in IMFA at the surface of the liquid
Tends to minimize the surface area of liquids (sphere) The Clausius-Clapeyron Equation
Makes molecules at surface pack closely together Gives the relationship between temperature and
Stronger the intermolecular forces, the higher the pressure
surface tension P1 ΔH vap 1 1
Increasing temperature decreases surface tension ln = ( − )
P2 R T2 T 1
In which:
-P1 and P2 are the vapor pressures at T1 and T2
respectively
-T is given in units Kelvin
-ln is the natural log
-R is the gas constant (8.314 J/K mol)
-∆Hvap is the molar heat of vaporization
Solids
Crystalline solids
-Atoms, ions or molecules are ordered in well-defined
arrangements (crystal lattice)
-Have a repeating unit known as a unit cell
Amorphous solids
-Particles have no orderly structure
Bonding in Solids
A. Molecular solids
Atoms or molecules held together by weak
intermolecular forces of attraction
Melting and Freezing
Fairly soft
A substance
Low to moderately high melting points (below 200oC)
-is melting while it changes from a solid to a liquid.
Poor thermal and electrical conduction
-is freezing while it changes from a liquid to a solid.
Examples
Water has a freezing (melting) point of 0°C.
-argon
-dry ice (solid CO2) Heat of Fusion, DHfus
-sugar The amount of heat needed to melt a solid (at its melting
B. Covalent network solids point).
Atoms held together by covalent bonds
Very hard H2O(s) ® H2O(l) DHfus = 6.01 Kj
Very high melting points
Poor thermal and electrical conduction How much heat in kJ is needed to melt 15.0 g of water?
Examples H2O(s) ® H2O(l) DHfus = 6.01 kJ
-Diamond (melting pt: 3550oC)
-graphite Sublimation
C. Ionic solids Occurs when particles change directly from solid to a
Ions held together by electrostatic forces of attraction gas.
Hard and brittle Typical of dry ice, which sublimes at -78oC.
High melting point Takes place in frost-free refrigerators.
Stronger the ionic bond, higher melting point Used to prepare freeze-dried foods for long-term
Poor thermal and electrical conduction storage.
Examples
Evaporation and Condensation
-NaCl (melting point: 801oC)
Water evaporates when molecules on the surface gain
-MgO (melting point: 2852oC)
sufficient energy to form a gas.
D. Metallic solids
Water condenses when gas molecules lose energy
Metal atoms held together by metallic bonds
and form a liquid.
Soft to very hard
Low to very high melting point Heat of Vaporization
Excellent thermal and electrical conduction The amount of heat absorbed to vaporize a liquid to
Malleable and ductile gas at the boiling point.
Examples
-Sodium (melting point: 97.5oC) H2O(l) ® H2O(g) DHvap = 40.7 kJ
-Chromium (melting point: 1890oC)
How much heat is released when 50.0 g of steam from a
Metallic Bonding: Electron Sea Model volcano condenses at 100°C?
The valence electrons of the metal’s atoms is spread H2O(l) ® H2O(g) DHvap = 40.7 kJ
out over all the metal
Essentially all the valence electrons belong to all the Heating Curve
atoms in the substance Illustrates the changes of state as a solid is heated.
Uses sloped lines to show an increase in temperature.
Phase Changes Uses plateaus (flat lines) to indicate a change of state.
Every phase change is accompanied by a change in the
energy of the system. Cooling Curve
Illustrates the changes of state as a gas is cooled.
Uses sloped lines to indicate a decrease in
temperature. which equilibria exist between the different states of
Uses plateaus (flat lines) to indicate a change of state. matter.
Such a diagram also allows us to predict which phase
of a substance is present at any given temperature and
pressure.
Calculate the enthalpy change upon converting 1.00 mol
of ice at -25 °C to steam at 125 °C under a constant
pressure of 1 atm.
Liquefaction of a Gas
A gas normally liquefies at some point when pressure
is applied.
Water vapor at 100 °C, liquefies at 760 torr.
At 110 °C, liquefies at 1075 torr
At 374 °C liquefies at 1.655 x 105 torr (217.7 atm)
Above this temperature no amount of pressure causes
a distinct liquid phase to form. Gases
Instead, as pressure increases, the gas becomes Properties of Gases
steadily more compressed. Gas expands spontaneously to fill its container
-No definite volume
Critical Temperature -Gases are highly compressible
The highest temperature at which a distinct liquid Form homogeneous mixtures with each other
phase can form regardless of the identities or relative proportions of the
Above the critical temperature, the kinetic energies of components
the molecules are greater than the attractive forces that Individual molecules are relatively far apart
lead to the liquid state regardless of how much the
substance is compressed to bring the molecules closer Pressure
together. Gases exhibit pressure on any container they are in.
The greater the intermolecular forces, the higher the Pressure is defined as a force per unit of area
critical temperature of a substance.
Atmospheric Pressure
Critical Pressure The atmosphere exerts pressure on the Earth that
The pressure required to bring about liquefaction at decreases with increasing altitude
the critical temperature. -This is due to the fact that with increasing altitude,
there is a decrease in the column of gases above the
Supercritical Fluid Earth’s surface
State achieved when the temperature of a substance Hydrostatics considers the pressure that is exerted by a
exceeds the critical temperature and the pressure fluid that is at rest.
exceeds the critical pressure, and the liquid and gas Using this as a frame of reference the atmospheric
phases become indistinguishable from each other pressure is viewed as a result of the mass of the column
Expands to fill its container (like a gas), but the of gases above the Earth.
molecules are still quite closely spaced (like a liquid) Using a molecular frame of reference, the atmospheric
Can behave as solvents dissolving a wide range of pressure is viewed as a result of the kinetic energy of
substances molecules and the force with which they strike an object.
-Supercritical fluid extraction= Supercritical CO2 Atmospheric pressure is actually a result of the
interaction between these two factors.
Phase Equilibria
The equilibrium between a liquid and its vapor is not 1 atmosphere (1 atm) = 760 mm Hg = 760 torr
the only dynamic equilibrium that can exist between
states of matter. Gas Laws
Under appropriate conditions, a solid can be in Boyle’s Law- The volume of a fixed quantity of gas
equilibrium with its liquid or even with its vapor. maintained at constant temperature is inversely
-The temperature at which solid and liquid phases proportional to the pressure.
coexist at equilibrium is the melting point of the solid or Charles’ Law- The volume of a fixed amount of gas
the freezing point of the liquid. maintained at constant pressure is directly proportional
Solids can also undergo evaporation and therefore to its absolute temperature.
possess a vapor pressure. STP Conditions- 1 atm , 0oC or 273 K
Gay-Lussac’s Law of Combining Volumes- At a given
Phase Diagrams pressure and temperature, the volumes of gases that
A graphic way to summarize the conditions under react with one another are in the ratios of small whole
numbers. Effusion- The escape of molecules through small holes
Avogadro’s Law- The volume of a gas maintained at in a barrier.
constant temperature and pressure is directly
proportional to the number of moles of gas. The heavier a gas, the slower it moves.
P V
n1T
1 P
= V
n12T22
12
Attractive forces come into play at high pressure and
low temperature.
These attractions lessen the force with which the
molecule hits the wall.
As a result, the gas pressure is less than that of an
Further Applications of Ideal Gas Equation ideal gas.
Density This effect decreases PV/RT to below its ideal value.
d= m/V = (P x MW)/RT At high pressures, gas volumes tend to be slightly
Molar Mass greater than those predicted by the ideal-gas equation.
MW= (d x RT)/P When the pressure is sufficiently high, the volume
effects dominate and PV/RT increases to above the ideal
Dalton’s Law of Partial Pressures value.
The total pressure of a mixture of gases equals the Behavior approximated by other equations
sum of the pressures that each would exert if it were -van der Waals equation
present alone. A real gas will behave like an ideal gas under the
Partial pressure – pressure exerted by a particular following conditions
component of a mixture of gases 1. Low pressure
Ptotal = P1 + P2 + P3 + … 2. High temperature
Ptotal = n1(RT/V) + n2 (RT/V) + n3 (RT/V) + …
Ptotal = (n1 + n2 + n3 +…)(RT/V) = ntot (RT/V) Van der Waals Equation
Spontaneous Processes
Processes in which the energy content of the system
decreases tend to occur spontaneously Solubility
-Exothermic processes are favorable The amount of a substance that dissolves in a given
However, there are also endothermic processes that quantity of solvent at a given temperature to form a
occur spontaneously. saturated solution.
-Example: NH4NO3 readily dissolves in water
Example: solubility of NaCl in water at 0oC is 35.7 g per
Characterized by an increase in disorder or
100 mL of water
randomness of the system
Processes in which the disorder of the system Unsaturated Solution
increases tend to occur spontaneously. Solution containing less solute than a saturated
-Unless the molecules are restrained by sufficiently solution.
strong intermolecular forces or by physical barriers
Supersaturated Solution
The process by which the solvent molecules surround Solutions that contain a greater amount of solute than
the solute molecules/ions is known as solvation. that is needed to form a saturated solution.
When the solvent is water, the process is referred to Prepared by saturating a solution at high temperature
as hydration. then carefully cooling it to room temperature at which the
solute is less soluble.
Enthalpy of Hydration
These solutions are unstable; crystallization can
The heat energy released when new interactions are
usually be stimulated by adding a “seed crystal” or
made between the ions and water molecules
scratching the side of the flask.
Always exothermic because ion-dipole forces are very
strong Factors affecting Solubility
Magnitude depends on the charge density, the ratio of A. Nature of Solute/Solvent
charge to volume. General Rule: Like dissolves like.
-The attractions are stronger the smaller the ion. -Polar/Ionic solutes dissolve in polar solvents.
-The attractions are stronger the more highly charged -Nonpolar solutes dissolve in nonpolar solvents.
the ion. B. Temperature
In general, solubility of solid solutes increases with
Energy Changes and Solution Formation increasing temperature.
The solubility of gases in water decreases with
increasing temperature.
C. Pressure
Solubility of a gas in any solvent is increased as the
pressure of the gas over the solvent increases.
Henry’s Law
Sg = kPg
D. Surface area
Powdered solutes dissolve more rapidly because
more surface is exposed to the solvent.
E.Agitation Vapor Pressure Depression
Rate of dissolution increases with stirring since fresh Because of solute-solvent intermolecular attraction,
solvent is continually coming in contact with the solute. higher concentrations of nonvolatile solutes make it
Also facilitates an increase in entropy. harder for solvent to escape to the vapor phase.
Therefore, the vapor pressure of a solution is lower
Ways of Expressing Concentration than that of the pure solvent.
Mass percentage (% by mass)
% (w/w) = grams solute__ x 100% Raoult’s Law
grams solution PA = XAPoA
Volume percentage (% by volume)
% (v/v) = volume solute__ x 100% Where
volume solution -XA is the mole fraction of compound A
ppm or ppb -PoA is the normal vapor pressure of A at that
1 ppm = grams solute x 106 (ppm) x109 (ppb) temperature
grams solution
NOTE: This is one of those times when you want to
make sure you have the vapor pressure of the solvent.
Mole fraction Ideal Solution- Any solution that obeys Raoult’s law
Xa = moles of A -Solute–solute, solvent–solvent, and solute– solvent
total moles in solution interactions are indistinguishable from one another
- In some applications, one needs the mole fraction of
solvent, not solute—make sure you find the quantity you Boiling Point Elevation and Freezing Point Depression
need! Nonvolatile solute-solvent interactions also cause
Molarity (M) solutions to have higher boiling points and lower freezing
M = moles solute___ points than the pure solvent.
Liter of solution Note that in both equations, DT does not depend on
what the solute is, but only on how many particles are
Molality (m) dissolved.
m= mol of solute
kg of solvent Boiling Point Elevation
The change in boiling point is proportional to the molality
-Because both moles and mass do not change with of the solution:
temperature, molality (unlike molarity) is not temperature
dependent. DTb = Kb m
Changing Molarity to Molality where Kb is the molal boiling point elevation constant, a
property of the solvent. DTb is added to the normal
boiling point of the solvent.
DTf = Kf m
Osmosis
Some substances form semipermeable membranes,
allowing some smaller particles to pass through, but
blocking other larger particles.
In biological systems, most semipermeable
membranes allow water to pass through, but solutes are
not free to do so.
In osmosis, there is net movement of solvent from the
area of higher solvent concentration (lower solute
concentration) to the are of lower solvent
concentration (higher solute concentration).
Osmotic Pressure
The pressure required to stop osmosis, known as
osmotic pressure, p, is
n
p=i( )RT = iMRT
V