Lesson 1: Gases Lesson 3: Solutions

Avogadro’ s Law CONCENTRATION

n1V2 = n2V1 Mole Fraction
Boyle’ s Law Xa = mol of component / sum of moles of
all component
P1V1 = P2V2
Molarity (M)
Charles’ Law
M = moles of solute / volume of solution (L)
V1T2 = V2T1
Molality (m)
Combined Gas Law
m = moles of solute / mass of solvent (kg)
P1V1T2 = P2V2T1
Dalton’ s Law
SOLUBILITY
Pa = XaPtot
Henry’ s Law
Gay-Lussac’ s Law
Cg = kPg
P1T2 = P2T1
Ideal Gas Law
COLLIGATIVE PROPERTIES
PV = nRT
Vapor Pressure Lowering
P1 = X1Po
STP: 273 K, 22.4 L, and 1 atm
Boiling Point Elevation
Gas Constant (R) = 0.0821 L*atm / mol*K
Tb - Tbo = Kbm
Avogadro’ s Constant = 6.022 x 1023 / mol
∆Tb = Kbm
Temperature = + 273 Kelvin (K)
Freezing Point Lowering
Volume = Liters (L)
Tf – Tfo = Kfm
Mass = Kilogram (kg)
∆Tf = Kfm
Pressure = atm (760 mmHg)
Osmotic Pressure
Π = MRT
Lesson 2: Liquids and Solids
• Electrolytes have a Van’t Hoff Factor
Clausius-Clapeyron Equation
Temperature = Celsius (oC)
𝑷𝟐 ∆𝑯𝒗𝒂𝒑 𝟏 𝟏
𝐥𝐧 ( ) = [ − ] Volume = Liters (L)
𝑷𝟏 𝑹 𝑻𝟏 𝑻𝟐
Mass = Kilogram (kg)

Gas Constant (R) = 8.31 J / mol*K

Lesson 1: Gases
INTRODUCTION
➢ The Greeks considered gases as one
of the four fundamental elements of
nature
➢ Lavoisier, Cavendish, and Priestly (18th
Century): Air is primarily nitrogen and
oxygen, with trace components of
argon, carbon dioxide and water
vapor
VOLUME, TEMPERATURE, AND PRESSURE
➢ A gas expands uniformly to fill the
container in which it is placed. Hence,
the volume of the container is the
volume of the gas.
➢ The temperature of gas must be
indicated on the Kelvin scale.
➢ Amount of gas is the number of moles.
➢ Atmospheric pressure is 14.7 psi
Barometer
• Measures pressure in terms of the
height of a column on liquid mercury
• Atmosphere exerts a force on a pool
of mercury, causing it to rise
• Mercury is used to keep the column a
manageable height
Manometer
• Measures gas pressure by differential
• Height of the column of liquid is
proportional to the pressure
Density
• Not an extensive property
• Depends on: pressure, temperature,
and molar mass
Vapor Pressure
• Pressure of the gaseous form of that
substance
• Intensive property
• Depends on temperature
*When a gas is collected over water, the total
pressure is the pressure of the gas plus the
vapor pressure of water
KINETIC THEORY OF GASES
1. Gases are mostly empty space. The total
volume of the molecules is small.
2. Gas molecules are in constant, random
motion,
3. Collisions of gas particles are elastic.
4. Gas pressure is caused by collisions of
molecules with the walls of container.
RESULTS FROM KINETIC ENERGY OF
TRANSLATIONAL MOTION
• At a given temperature, all molecules
of all gases have the same average
kinetic energy of translational motion
• The average kinetic energy of a gas
particle is directly proportional to the
Kelvin temperature
EFFUSION OF GASES
Diffusion
• Gases move through space from a
region of high concentration to a
region of low concentration
Effusion
• Gas particles will escape through a
small hole (orifice) in a container
DISTRIBUTION OF MOLECULAR SPEEDS
• At a given temperature, gas particles
will have a set of speeds, not a single
fixed value for speeds
• As the temperature increases, the
maximum shifts toward higher speed
and the relative number of molecules
at that speed decreases
REAL GASES
• Molar volume of a real gas is less than
that calculated by the ideal gas law
• Two factors that are important
o The attractive forces between
gas particles
o The volume of the gas
particles
o NOTE: Both are ignored by
ideal gas law
Attractive Forces
• The observed molar volume for gases
is lower than that calculated by the
ideal gas law
o The forces between particles
pull the particles together
o The volume occupied by the
gas is then decreased
o This is a negative deviation
from the ideal gas law
Particle Volume
• Up to 150 atm, the deviation from
ideality steadily increases
• The volume of the gas particles
becomes a more significant factor in
determining the volume of the gas as
the pressure increases
LIQUEFACTION OF GASES
• All gases can be liquefied
o Lowering the temperature
o Increasing the pressure
• When a gas is liquefied, the attractive
forces between gas particles becomes
significant
• The closer a gas is to the liquid state,
the more it will deviate from the ideal
gas law
SUMMARY:
• Use the ideal gas law to:
o Solve initial and final state
problems
o Solve single-state problems
o Calculate the density of a gas
o Relate amounts of gases in
reactions
• Graham’s Law is used to relate the
rate of effusion to the molar mass of a
gas:
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑜𝑓 𝐵 𝑀𝑀𝐴 ½
=( )
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑀𝑀𝐵
Lesson 2: Liquids and Solids
RECALL:
• At ordinary temperatures and
pressures, all gases follow the ideal
gas law
• There is no equivalent equation of
state that can be written to correlate
the properties of liquids and solids
LIQUIDS AND SOLIDS DIFFER FROM GASES
1. Molecules are much closer together in
liquids and solids than in gases
• In gases, molecules are separated by
ten or more molecular diameters
• In liquids and solids, the molecules are
in contact with each other
2. Intermolecular forces play a major role in
the behavior of liquids and solids, whereas
they are negligible in gases.
LIQUID-VAPOR EQUILIBRIUM
Vaporization
• Liquid is converted to gas
• In an open container, evaporation
continues until all the liquid is
converted to vapor
• In a closed container, the process of
vaporization is countered by the
process of condensation
Equilibrium
• Dynamic equilibrium is established
when the rate at which the liquid
vaporizes is equal to the rate at which
the vapor condenses
• The liquid level in the container does
not change
• Molecules enter the vapor phase from
the liquid and condense from the
vapor phase to the liquid at the same
rate
Vapor Pressure
• Once equilibrium and vapor are
reached, the number of molecules per
unit volume does not change with
time
• The pressure exerted by the vapor
over the liquid remains constant
• The vapor pressure is temperature
dependent
NOTE: As long as both liquid and vapor are
present, the vapor pressure is independent of
the volume of the container.
VAPOR PRESSURE AND TEMPERATURE
• The vapor pressure of a liquid
increases as the temperature rises
• Increase in pressure is not linear with
temperature
∆𝐻𝑣𝑎𝑝
ln 𝑃 = − +𝑏
𝑅𝑇
Boiling Point
• When heat is applied to a liquid in an
open container, bubbles eventually
form at the bottom
• The temperature at which liquid boils
depends on the pressure above it
• The boiling point is the temperature at
which the vapor pressure equals the
prevailing pressure
• At high elevation, atmospheric
pressure is lower, so the boiling point
is lower
CRITICAL TEMPERATURE AND PRESSURE
• For every liquid, there is a
temperature above which only vapor
can exist. This is critical temperature.
• At this temperature, the pressure is
called the critical pressure.
• Together, they are called the critical
point
Permanent Gases • Curve AB is the vapor pressure-
temperature curve
• Substances with critical temperatures • Curve AC is the vapor pressure curve
below 25oC of ice
• Usually stored in cylinders at 150 atm • Line A-D gives the temperature-
or above pressure dependence for ice in
• Only vapor is present in the tank equilibrium with water
• Pressure in the tank drops as the gas • Point A is the triple point
is released o All three phases are in
Condensable Gases equilibrium
o There is only one triple point
• Have critical temperatures above for a pure substance
25oC o For water, the triple point is at
o Carbon dioxide 0.01oC
o Hydrocarbon gases
o Ammonia Sublimation
o Chlorine • Process by which a solid pass directly
o Sulfur dioxide into the vapor phase without first
• For these substances, the liquid- being converted to a liquid
vapor equilibrium accounts for the • Can only happen at a temperature
pressure in the tank below the triple point
• Pressure will not change until all the • Water can sublime if the pressure is
liquid is gone reduced
o Freeze drying
o Cold winter days
PHASE DIAGRAMS • Iodine sublimes readily because its
• They are graphical representations of triple point pressure is much higher
than that of water
the pressure and temperature
dependence of pure substance Melting Point
o Pressure on y-axis
o Temperature on x-axis • For a pure substance, the melting
• Consider these three places: point and freezing point are identical
o In a region, one phase exists • The effect of pressure on the freezing
o On a line, two phases exist in point is very small
equilibrium • An increase in pressure favors the
o At a point, three phases exist denser phase
in equilibrium o Water is denser than ice, so it
is anomalous
 • Positive slope: solid is denser than
liquid
• Negative slope: liquid is denser than
solid
MOLECULAR SUBSTANCES: Intermolecular
Forces
• Many gases, most liquids and many
more solids are molecular
• Molecules are the structural units of
such matter
• Properties of molecular substances
include:
o They are nonconductors of
electricity when pure
o They are insoluble in water but
soluble in nonpolar solvents
such as benzene
o They have low melting point
Dispersion Forces
• All substances have dispersion forces
• Also called London or van der Waals
forces
• Stem from induced dipoles in
molecules
• Motion of electrons in the molecule
causes transient dipoles to form
• Increase with the number of electrons
in the molecule
• As molar mass increases, dispersion
forces become stronger
Dipole Forces
• Molecules with permanent dipoles
display dipole forces
• Dispersion forces are present but
weak
• Adjacent molecules line up so that the
negative pole of one molecule is as
close as possible to the positive pole of
another molecule
• Result is an electrostatic attractive
force that causes molecules to
associate with each other
Hydrogen Bonding
• Unusually strong type of dipole force
• H attached to a N, O, or F
• The H of one molecule can bond to the
negative end of the dipole of another
o Dipole arises from the
difference in the
electronegativity between H
and N, O, or F
• Results to high boiling points
Water
• Hydrogen bonding accounts for
o High specific heat
o High boiling point
o Higher density of the liquid
phase relative to the solid
COVALENT BOND VS. INTERMOLECULAR
FORCES
Three types of intermolecular force:
• Dispersion
• Dipole
• Hydrogen bond
NOTE: All three intermolecular forces are
weak relative to the strength of a covalent
bond
Network Covalent Solids
• Continuous network of covalent
bonds
• Crystal is one large molecule
Characteristics:
• High melting points, often above
1000oC
• Covalent bonds must be broken to
melt the substance
Examples:
• Graphite and diamond allotropes
Ionic Solids CRYSTAL STRUCTURES
• Oppositely-charged ions held • Solids crystallize into definite
together by strong electrical forces geometric forms
Characteristics: Crystal Building Blocks
• Nonvolatile; high melting points at • Crystals have definite geometric
600-2000oC forms because the atoms or ions are
• Nonconductors of electricity in the arranged in definite, three-
solid state dimensional patterns.
o Conduct when melted or • Metals crystallize into one of three
dissolved in water unit cells
• Many are soluble in water but not in
nonpolar solvents 1. Simple Cubic (SC): eight atoms at the
corners
Strengths:
2. Face centered cubic (FCC): simple cubic
• Charges of the ions plus one atom in the center of each face
o Higher charges produce
stronger bonds 3. Body-centered cubic (BCC): simple cubic
• Sizes of the ions plus one atom in the center of the cube
o Smaller internuclear distance
result in stronger bonds
Metallic Solids
• Structural unit are +1, +2, and +3
metals with associated electrons
Characteristics:
• High electrical conductivity
o Highly mobile electrons in
structure
• High thermal conductivity
o Heat is carried through the
structure by collision between
electrons
• Ductility and malleability
o Can be drawn into wire or
hammered into sheets
• Luster
• Three other ways to look at the
o Polished metal surfaces reflect
crystalline unit cells:
light
• Insolubility in water and other 1. Number of atoms per unit cell
common solvents
2. Relation between side of cell(s) and radius
of atom or ion(r)
3. Percentage of empty space
Ionic Crystals
• Geometry of ionic crystals is more
difficult to describe than that of
metals
o LiCl forms face-centered
cube with Li+ ions in the
“ holes” between the
anions
o NaCl are slightly too large
to fit into the holes
between the anions, so Cl-
ions are pushed apart
slightly

SUMMARY:
• Use ideal gas law to determine
whether a liquid will completely
vaporize in a sealed container
• Use the Clausius-Clapeyron
equation to relate vapor pressure
to temperature
• Use a phase diagram to
determine the phases present
given the pressure and
temperature
Lesson 3: Solutions
CONCENTRATION UNITS
Molarity (M)
• Moles of solute per liter of solution
Mole Fraction (X)
• Mole fraction of A is the number of
moles of A divided by the total
number of moles
• The mole fractions of all components
must add to 1
Molality (m)
• Number of moles of solute per
kilogram of solvent
CONVERSION BETWEEN CONCENTRATION
UNITS
Mass percent = 100 g solution
Molarity (M) = 1.00 L solution
Molality (m) = 1.00 kg solvent
Mole fraction (X) = 1.00 mol solution
PRINCIPLES OF SOLUBILITY
• The extent to which a solute dissolve
in a solvent depends on several
factors:
o The nature of solvent and
solute particles and the
interaction between them
o The temperature at which the
solution forms
o The pressure, in cases of
gaseous solutes
Solute-Solvent Interactions
• Like dissolves like
o Polar solutes dissolve in polar
solvents
o Nonpolar solutes dissolve in
nonpolar solvents
• Nonpolar substances have poor
affinity for water
o Petroleum
o Hydrocarbons
• Polar substances dissolve easily in
water
o Alcohols
o Solubility of alcohols
decreases as the molar mass
of the alcohol increases
Solubility of Vitamins
• Some vitamins are readily water
soluble
o OH groups can form hydrogen
bonds with water
o Vitamins B and C are water-
soluble examples
• Some vitamins are nonpolar and
therefore not soluble in water
o Vitamins A, D, E, and K
o These are soluble in body fats,
which are largely nonpolar in
character
Solubility of Ionic Compounds
• The solubility of ionic compounds in
water varies tremendously from one
solid to another
• Two forces must be balanced
o The force of attraction
between water molecules and
ions: the stronger the force,
the greater the tendency
toward solution
o The force of attraction
between oppositely charged
ions: the stronger the force,
 the more likely the solute will
stay in the solid state
Temperature and Solubility
• When a solute dissolves, equilibrium
is established
• An increase in temperature always
shifts the equilibrium to favor the
endothermic process
o Dissolving a solid in a liquid is
usually an endothermic
process
o Solubility tends to increase
with temperature for most
solids
• For a gas, the dissolution process is
exothermic, so the reverse process
(gas to solution) is endothermic
• Therefore, for gases, solubility
decreases with increasing
temperature
PRESSURE AND SOLUBILITY
• Pressure has a major effect on the
solubility of a gas in a liquid, but little
effect on other systems
• At low to moderate pressure, the
concentration of a gas increases with
the pressure (Henry’s Law)
• Carbonated beverages
o Pressure of carbon dioxide is
kept high by pressurizing the
container
o Releasing the pressure causes
the beverage to go flat;
carbon dioxide bubbles out of
the solution
• Deep-sea diving
o Increased pressure while
diving increases gas solubility
in bodily fluids
o Rising too rapidly to the
surface can lead to bubbling
of gas forming in the blood
and other fluids in the body,
this is called bends
COLLIGATIVE PROPERTIES OF
NONELECTROLYTES
• Properties of solution differ from pure
solvent
• Some properties depend on the
concentration of dissolved particles
and not on their nature
o These are colligative
properties
o Physical description of these
properties is limiting laws:
they are approached as the
solution becomes more dilute
Vapor Pressure Lowering
- Independent of the nature of the
solute but dependent on the
concentration
- Vapor pressure of a solvent over a
solution is always lower than the
vapor pressure of a pure solvent
Boiling Point Elevation
- When a solution of a nonvolatile solute
is heated, it does not boil until the
temperature exceeds the boiling point
of the pure solvent
Freezing Point Lowering
- When a solution of a nonvolatile solute
is cooled, it does not freeze until a
temperature below the freezing point
of the pure solvent is reached
Boiling and Freezing Point Alteration
• Boiling point elevation and freezing
point lowering are both dependent on
the concentration of the solute in
molality
Automotive Applications
• The coolant/antifreeze in an
automobile is a direct application of
the boiling point elevation and
freezing point lowering
OSMOSIS
Semi-Permeable Membranes
• Consider the concentration of solvent
in a solution
o Concentration is lower than it
is for the pure solvent
o Solvent will flow from an area
of high concentration to an
area of low concentration
• Next consider a semi-permeable
membrane
o Allows water and small
molecules to pass, but not
larger molecules
o Water will flow from high to
low concentration
o The process is called osmosis.
Evaporation and Condensation
• The difference in concentration of
solvent between a beaker of pure
water and one of a solution will cause
the liquid level in the solution to rise,
while the level in the beaker
containing water will fall
o Vapor pressure is higher over
pure water
o Water is transferred to the
beaker containing the solution
Osmotic Pressure (π)
- Pressure required to prevent osmosis
from occurring
- The flow of solvent causes the
pressure
- Applying a pressure greater than π
will cause the water to flow in the
other direction; this is reverse osmosis
- Reverse osmosis can be used to
prepare fresh water from seawater
- It depends on molarity
Osmolarity
- Solutions of the same osmotic
pressure are said to be osmolar
- Important to medical applications
- In red blood cells
o Hemolysis: concentration of
ions is larger inside the cell,
water will flow in, causing the
cell to burst
o Crenation: concentration of
ions is larger outside the cell,
water will flow out, causing the
cell to shrivel
COLLIGATIVE PROPERTIES OF
ELECTROLYTES
• Since an electrolyte will produce more
than one mole of ions per mole of
compound dissolved, the colligative
effect should be larger than that of a
nonelectrolyte of the same
concentration
Deliquescence
- P is so large that the solid will pick up
moisture from the air and dissolves
- When relative humidity exceeds 30%,
calcium chloride can actually dissolve
in the water it picks up
Van’ t Hoff i-factor: Limiting
- Number of moles of particles per mole
of solute
SUMMARY:

• Apply Henry’s law to relate gas

solubility to partial pressure
• Apply Raoult’s law to calculate vapor
pressure lowering
• Use colligative properties to
determine the molar mass of solute
and determine the extent of ionization

EXTRA NOTES:

• Gases use Kelvin for temperature,

other compounds use oC