Liquids, Solids and Phase Changes -Polarizability – measure of the “squashiness” of a

molecule’s electron cloud

Kinetic Molecular View of Liquids and Solids -Increases with molecular weight
All real gases can be condensed to liquids by -For molecules of comparable weights, elongated
lowering the temperature and increasing the pressure shapes are more polarizable
-Decreases the average speed of the molecules
-When moving slow enough, they will be attracted to
each other and form a liquid
Further decrease in temperature and increase in
pressure will further decrease average speed of
molecules
-Attraction between molecules will be strong enough to
lock molecules in place, forming a solid

C.Hydrogen bonding
- Exist when a H is directly bonded to a highly
electronegative atom (F, O, N)
- Attraction forms between the hydrogen atom and a
Characteristics of Liquids and Solids nearby electronegative ion or atom
Liquids - Much stronger than van der Waals forces
Denser and less compressible than gases - Between 4-25 kJ/mole
Have definite volume - Explains why ice floats on water
Can be poured - Explains why water expands when it freezes
Take shapes of their containers - Hexagonal shapes of snowflakes
Solids
Denser and less compressible than liquids
Retains own shape and volume Ionic compounds in polar solutions
-Ion-dipole- Found in solutions of ionic substances in
ntermolecular Forces polar liquids. Example: NaCl in water
Determine the physical properties of substances
Only 15% as strong as covalent or ionic bonding
3 types exist between neutral molecules
A. Dipole-dipole
-Exist between neutral polar molecules
-Generally weaker than ion-dipole forces
-For molecules of approximately equal size and
mass, the strengths of intermolecular attractions
increase with increasing polarity

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. London forces B. Wide difference in molecular weights and no H-
-Form when an instantaneous dipole induces a dipole
bonding
attraction between molecules
Dispersion forces dominate
-Operate between ALL kinds of molecules
-Higher MW, stronger IMFA
-Relatively weak
 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
Increasing temperature decreases viscosity
Substances with high vapor pressure evaporate more
Which of the following pairs of substances will be more quickly than substances with low vapor pressure
viscous? -Stronger the IFA, the lower the vapor pressure
Br2 or N2 = Br2 HCl or HBr= HBr Liquids that readily evaporate are said to be volatile
CO2 or HCl= HCl Vapor pressure increases with increasing temperature
B. Surface tension
Energy required to increase the surface area of a Which of the following pairs of substances will have the
liquid by a unit amount higher vapor pressure?
Due to imbalance in IMFA at the surface of the liquid CH4 or H2O = CH4 HCl or HF = HF
Tends to minimize the surface area of liquids (sphere) Br2 or N2 = N2
Makes molecules at surface pack closely together
Stronger the intermolecular forces, the higher the The Clausius-Clapeyron Equation
surface tension Gives the relationship between temperature and
Increasing temperature decreases surface tension pressure
P1 H vap 1 1
ln  (  )
P2 R T2 T1
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

Which of the following pairs of substances will have the Example: The vapor pressure of water is 1.0 atm at 373
higher surface tension? K, and the enthalpy of vaporization is 40.7 kJ/mol.
CH4 or H2O = H2O HCl or HF= HF Estimate the vapor pressure at 363 K and 383 K
respectively.
B.1. Capillary action
Rise of liquids up very narrow tubes D. Boiling point
-Cohesive forces -Forces that bind like molecules Liquids boil when its vapor pressure equals the
together external pressure acting on the surface of the liquid
- Adhesive forces- Forces that bind a substance to a - Bubbles form within the interior of the liquid
surface Dependent on pressure
Normal Boiling Point- Boiling point of a liquid at 1 atm
pressure
 The more volatile the liquid, the lower is its boiling
point.
Which of the following pairs of substances will have the
higher boiling point?
Br2 or N2 = N2 HCl or HBr = HBr
CO2 or HCl= HCl CH4 or H2O = H2O
HCl or HF = HF

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, Hfus
-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) Hfus = 6.01 Kj
Very high melting points
How much heat in kJ is needed to melt 15.0 g of water?
Poor thermal and electrical conduction
Examples H2O(s)  H2O(l) Hfus = 6.01 kJ
-Diamond (melting pt: 3550oC)
Sublimation
-graphite
Occurs when particles change directly from solid to a
C. Ionic solids
gas.
Ions held together by electrostatic forces of attraction
Typical of dry ice, which sublimes at -78oC.
Hard and brittle
Takes place in frost-free refrigerators.
High melting point
Used to prepare freeze-dried foods for long-term
Stronger the ionic bond, higher melting point
storage.
Poor thermal and electrical conduction
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) Hvap = 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) Hvap = 40.7 kJ
out over all the metal
Heating Curve
Essentially all the valence electrons belong to all the
Illustrates the changes of state as a solid is heated.
atoms in the substance
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
Cooling Curve
energy of the system.
Illustrates the changes of state as a gas is cooled.
Uses sloped lines to indicate a decrease in
temperature.
Uses plateaus (flat lines) to indicate a change of state.
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.
What is the enthalpy change during the process in which
100.0 g of water at 50.0 °C is cooled to ice at -30.0 °C?
The specific heats of ice, liquid water, and steam are
2.03, 4.18, and 1.84 J/g-K, respectively.
For H2O, Hfus = 6.01 kJ/mol and Hvap = 40.67 kJ/mol.
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.
Instead, as pressure increases, the gas becomes
steadily more compressed.
Critical Temperature
The highest temperature at which a distinct liquid
phase can form
Above the critical temperature, the kinetic energies of
the molecules are greater than the attractive forces that
lead to the liquid state regardless of how much the
substance is compressed to bring the molecules closer
together.
The greater the intermolecular forces, the higher the
critical temperature of a substance.
Critical Pressure
The pressure required to bring about liquefaction at
the critical temperature.
Supercritical Fluid
State achieved when the temperature of a substance
exceeds the critical temperature and the pressure
exceeds the critical pressure, and the liquid and gas
phases become indistinguishable from each other
Expands to fill its container (like a gas), but the
molecules are still quite closely spaced (like a liquid)
Can behave as solvents dissolving a wide range of
substances
-Supercritical fluid extraction= Supercritical CO2
Phase Equilibria
The equilibrium between a liquid and its vapor is not
the only dynamic equilibrium that can exist between
states of matter.
Under appropriate conditions, a solid can be in
equilibrium with its liquid or even with its vapor.
-The temperature at which solid and liquid phases
coexist at equilibrium is the melting point of the solid or
the freezing point of the liquid.
Solids can also undergo evaporation and therefore
possess a vapor pressure.
Phase Diagrams
A graphic way to summarize the conditions under
which equilibria exist between the different states of
matter.
Such a diagram also allows us to predict which phase
of a substance is present at any given temperature and
pressure.
Gases
Properties of Gases
Gas expands spontaneously to fill its container
-No definite volume
-Gases are highly compressible
Form homogeneous mixtures with each other
regardless of the identities or relative proportions of the
components
Individual molecules are relatively far apart
Pressure
Gases exhibit pressure on any container they are in.
Pressure is defined as a force per unit of area
Atmospheric Pressure
The atmosphere exerts pressure on the Earth that
decreases with increasing altitude
-This is due to the fact that with increasing altitude,
there is a decrease in the column of gases above the
Earth’s surface
Hydrostatics considers the pressure that is exerted by a
fluid that is at rest.
Using this as a frame of reference the atmospheric
pressure is viewed as a result of the mass of the column
of gases above the Earth.
Using a molecular frame of reference, the atmospheric
pressure is viewed as a result of the kinetic energy of
molecules and the force with which they strike an object.
Atmospheric pressure is actually a result of the
interaction between these two factors.
1 atmosphere (1 atm) = 760 mm Hg = 760 torr
Gas Laws
Boyle’s Law- The volume of a fixed quantity of gas
maintained at constant temperature is inversely
proportional to the pressure.
Charles’ Law- The volume of a fixed amount of gas
maintained at constant pressure is directly proportional
to its absolute temperature.
STP Conditions- 1 atm , 0oC or 273 K
 Gay-Lussac’s Law of Combining Volumes- At a given
pressure and temperature, the volumes of gases that
react with one another are in the ratios of small whole
numbers.
Avogadro’s Law- The volume of a gas maintained at
constant temperature and pressure is directly
proportional to the number of moles of gas.
 -Equal volumes of gases at the same temperature and
pressure contain equal numbers of molecules.
-Experiments show that 1 mol of any gas at STP
occupies approximately 22.4 L
-1 mole = 6.02 x 1023 molecules = 22.4 L at STP
(Molar volume)
Ideal gas equation- PV = nRT
General Gas Equation- Use when comparing a gas
under two different conditions
-Cancel out the parameters that are held constant
Further Applications of Ideal Gas Equation
Density
d= m/V = (P x MW)/RT
Molar Mass
MW= (d x RT)/P
Dalton’s Law of Partial Pressures
The total pressure of a mixture of gases equals the
sum of the pressures that each would exert if it were
present alone.
Partial pressure – pressure exerted by a particular
component of a mixture of gases
Ptotal = P1 + P2 + P3 + …
Ptotal = n1(RT/V) + n2 (RT/V) + n3 (RT/V) + …
Ptotal = (n1 + n2 + n3 +…)(RT/V) = ntot (RT/V)
Real Gases
Not point masses
Do not travel in straight line motion
Have finite volumes
Do attract one another
The extent to which a real gas departs from ideal
behavior can be seen by PV/RT = n
-This form of the equation tells us that for 1 mol of
ideal gas, the quantity PV/RT equals 1 at all pressures.
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
ideal gas.
This effect decreases PV/RT to below its ideal value.
At high pressures, gas volumes tend to be slightly
greater than those predicted by the ideal-gas equation.
When the pressure is sufficiently high, the volume
effects dominate and PV/RT increases to above the
ideal value.
Behavior approximated by other equations
-van der Waals equation
A real gas will behave like an ideal gas under the
following conditions
1. Low pressure
2. High temperature
Van der Waals Equation

Partial Pressures and Mole Fractions

Kinetic Molecular Theory Accounts for attractive Accounts for the small
Gases consist of large numbers of molecules that are forces that tend to but finite volume
in constant, random, straight-line motion. decrease pressure occupied by the gas
The volume of all the molecules of the gas is molecules
negligible compared to the total volume in which the gas
is contained. Solutions
Attractive and repulsive forces between gas molecules
Homogeneous Mixtures
are negligible.
Solute
Collisions between molecules and the walls of the
Solvent
container are perfectly elastic.
Can exist in any of the 3 states
The average kinetic energy of the molecules is
A. Solid solutions
proportional to absolute temperature.
-Dental fillings, 14 K gold, sterling silver
Pressure of a gas is caused by collisions of the
B. Liquid solutions
molecules with the walls of container.
-Saline, vodka, vinegar, sugar water
-Frequency of collisions
C. Gaseous solutions
-How hard molecules hit the walls of the container
-Atmosphere, anesthesia gases
Examples
-Effect of volume increase at constant temperature The Solution Process
-Effect of a temperature increase at constant volume A solution forms when one substance disperses
uniformly throughout another.
Diffusion- The random and spontaneous mixing of
Depends on:
molecules.
A. The natural tendency of substances to mix and
Effusion- The escape of molecules through small holes
spread into larger volumes when not restrained in some
in a barrier.
way
The heavier a gas, the slower it moves. B. Intermolecular forces between like molecules and
unlike molecules
𝑅𝑎𝑡𝑒 1 𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠 2 -The intermolecular forces between solute and
=√
𝑅𝑎𝑡𝑒 2 𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠 1 solvent particles must be strong enough to compete with
those between solute particles and those between
solvent particles.
Solution Formation, Spontaneity and Disorder
Two factors to consider in a spontaneous process
Energy, H
Entropy, S
Spontaneous Processes
Processes in which the energy content of the system
decreases tend to occur spontaneously
-Exothermic processes are favorable
However, there are also endothermic processes that
occur spontaneously.
-Example: NH4NO3 readily dissolves in water
Characterized by an increase in disorder or
randomness of the system
Processes in which the disorder of the system
increases tend to occur spontaneously.
-Unless the molecules are restrained by sufficiently
strong intermolecular forces or by physical barriers
The process by which the solvent molecules surround
the solute molecules/ions is known as solvation.
When the solvent is water, the process is referred to
as hydration.
Enthalpy of Hydration
The heat energy released when new interactions are
made between the ions and water molecules
Always exothermic because ion-dipole forces are very
strong
Magnitude depends on the charge density, the ratio of
charge to volume.
-The attractions are stronger the smaller the ion.
-The attractions are stronger the more highly charged
the ion.
Energy Changes and Solution Formation
Hsoln = H1 + H2 + H3
Saturated Solutions
A solution in which undissolved solute and dissolved
solute are in equilibrium
rate of dissolution = rate of crystallization
Solute + solvent  solution
Solubility
The amount of a substance that dissolves in a given
quantity of solvent at a given temperature to form a
saturated solution.
Example: solubility of NaCl in water at 0oC is 35.7 g per
100 mL of water
Unsaturated Solution
Solution containing less solute than a saturated
solution.
Supersaturated Solution
Solutions that contain a greater amount of solute than
that is needed to form a saturated solution.
Prepared by saturating a solution at high temperature
then carefully cooling it to room temperature at which the
solute is less soluble.
These solutions are unstable; crystallization can
usually be stimulated by adding a “seed crystal” or
scratching the side of the flask.
Factors affecting Solubility
A. Nature of Solute/Solvent
General Rule: Like dissolves like.
-Polar/Ionic solutes dissolve in polar solvents.
-Nonpolar solutes dissolve in nonpolar solvents.
B. Temperature
In general, solubility of solid solutes increases with
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.
Gases in Solution- In general, the solubility of gases in
water increases with increasing mass.
-Larger molecules have stronger dispersion forces.
Henry’s Law
Sg = kPg
where Sg is the solubility of the gas;
k is the Henry’s law constant for that gas in that solvent;
Pg is the partial pressure of the gas above the liquid.
D. Surface area
Powdered solutes dissolve more rapidly because
more surface is exposed to the solvent.
E.Agitation
Rate of dissolution increases with stirring since fresh
solvent is continually coming in contact with the solute.
Also facilitates an increase in entropy.
Ways of Expressing Concentration
Mass percentage (% by mass)
% (w/w) = grams solute__ x 100%
grams solution
Volume percentage (% by volume)
% (v/v) = volume solute__ x 100%
volume solution
ppm or ppb
1 ppm = grams solute x 106 (ppm) x109 (ppb)
grams solution
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, T does not depend on
what the solute is, but only on how many particles are
Molality (m) dissolved.
m= mol of solute
Boiling Point Elevation
kg of solvent
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. Tb = Kb  m

Changing Molarity to Molality where Kb is the molal boiling point elevation constant, a
property of the solvent. Tb is added to the normal
boiling point of the solvent.

Freezing Point Depression

The change in freezing point can be found similarly:

Tf = Kf  m

Here Kf is the molal freezing point depression constant

of the solvent. Tf is subtracted from the normal freezing
point of the solvent.

Colligative Properties of Electrolytes

If we know the density of the solution, we can calculate
the molality from the molarity, and vice versa.
Since these properties depend on the number of
particles dissolved, solutions of electrolytes (which
dissociate in solution) should show greater changes than
those of nonelectrolytes.
Reassociation is more likely at higher concentration.
Therefore, the number of particles present is
concentration dependent.

Colligative Properties van’t Hoff Factor

Changes in colligative properties depend only on the Measure of the extent to which electrolytes dissociate
number of solute particles present, not on the identity of Ratio of the actual value of a colligative property to the
the solute particles. value calculated assuming the substance to be a
Among colligative properties are nonelectrolyte
-Vapor pressure depression We modify the previous equations by multiplying by
-Boiling point elevation the van’t Hoff factor, i
-Freezing point depression
-Osmotic pressure Tf = Kf  m  i or Tb = Kb  m  i

Vapor Pressure Depression
Because of solute-solvent intermolecular attraction,
higher concentrations of nonvolatile solutes make it
harder for solvent to escape to the vapor phase.
 Therefore, the vapor pressure of a solution is lower
than that of the pure solvent.
Raoult’s Law
PA = XAPoA
Where
-XA is the mole fraction of compound A
-PoA is the normal vapor pressure of A at that
temperature
NOTE: This is one of those times when you want to
make sure you have the vapor pressure of the solvent.
The ideal value of i can be determined for a salt by
noting the number of ions per formula unit
In the absence of info for actual value of i, may use
ideal value for calculations
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, , is
𝑛
 = i (𝑉 )RT = iMRT

where M is the molarity of the solution and R is the

universal gas constant and i is the van’t Hoff factor
- If the osmotic pressure is the same on both sides of a
membrane (i.e., the concentrations are the same), the
solutions are isotonic.

Osmosis in Blood Cells

 If the solute concentration outside the cell is greater
than that inside the cell, the solution is hypertonic. Water
will flow out of the cell, and crenation results.
 If the solute concentration outside the cell is less
than that inside the cell, the solution is hypotonic.Water
will flow into the cell, and hemolysis results.

Molar Mass from Colligative Properties

1. Lysozyme is an enzyme that breaks bacterial cell
walls. A solution containing 0.150 g of this enzyme in
210 mL of solution has an osmotic pressure of 0.953 torr
at 25 °C. What is the molar mass of lysozyme?

2. Adrenaline is the hormone that triggers the release of

extra glucose molecules in times of stress or emergency.
A solution of 0.64 g of adrenaline in 36.0 g of CCl4
elevates the boiling point by 0.49 °C. Calculate the
approximate molar mass of adrenaline from this data.