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Liquids, Solids and Phase Changes

Kinetic Molecular View of Liquids and Solids


All real gases can be condensed to liquids by
lowering the temperature and increasing the pressure
-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 -Polarizability – measure of the “squashiness” of a
molecule’s electron cloud
lock molecules in place, forming a solid -Increases with molecular weight
-For molecules of comparable weights, elongated
shapes are more polarizable

Characteristics of Liquids and Solids


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

B. London forces
-Form when an instantaneous dipole induces a dipole

attraction between molecules


-Operate between ALL kinds of molecules
-Relatively weak

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

Example: The vapor pressure of water is 1.0 atm at 373


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

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, DHfus = 6.01 kJ/mol and DHvap = 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. 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.

-Equal volumes of gases at the same temperature and


Rate 1
Rate 2
=

Molar Mass 2
Molar Mass 1

pressure contain equal numbers of molecules.


-Experiments show that 1 mol of any gas at STP
Real Gases
occupies approximately 22.4 L
Not point masses
-1 mole = 6.02 x 1023 molecules = 22.4 L at STP
Do not travel in straight line motion
(Molar volume)
Have finite volumes
Ideal gas equation- PV = nRT
Do attract one another
General Gas Equation- Use when comparing a gas
The extent to which a real gas departs from ideal
under two different conditions
behavior can be seen by PV/RT = n
-Cancel out the parameters that are held constant
-This form of the equation tells us that for 1 mol of
ideal gas, the quantity PV/RT equals 1 at all pressures.

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

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
are negligible. Homogeneous Mixtures
Collisions between molecules and the walls of the Solute
container are perfectly elastic. Solvent
The average kinetic energy of the molecules is Can exist in any of the 3 states
proportional to absolute temperature. A. Solid solutions
Pressure of a gas is caused by collisions of the -Dental fillings, 14 K gold, sterling silver
molecules with the walls of container. B. Liquid solutions
-Frequency of collisions -Saline, vodka, vinegar, sugar water
-How hard molecules hit the walls of the container C. Gaseous solutions
Examples -Atmosphere, anesthesia gases
-Effect of volume increase at constant temperature
-Effect of a temperature increase at constant volume The Solution Process
A solution forms when one substance disperses
Diffusion- The random and spontaneous mixing of uniformly throughout another.
molecules. Depends on:
A. The natural tendency of substances to mix and
spread into larger volumes when not restrained in some
way
B. Intermolecular forces between like molecules and
unlike molecules
-The intermolecular forces between solute and
solvent particles must be strong enough to compete with
those between solute particles and those between Saturated Solutions
solvent particles. A solution in which undissolved solute and dissolved
solute are in equilibrium
Solution Formation, Spontaneity and Disorder
Two factors to consider in a spontaneous process rate of dissolution = rate of crystallization
Energy, DH
Entropy, DS Solute + solvent D solution

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.

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

DHsoln = DH1 + DH2 + DH3 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 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 ž 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.

Freezing Point Depression


The change in freezing point can be found similarly:

DTf = Kf ž m

Here Kf is the molal freezing point depression constant


of the solvent. DTf is subtracted from the normal freezing
point of the solvent.

Colligative Properties of Electrolytes


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
If we know the density of the solution, we can calculate concentration dependent.
the molality from the molarity, and vice versa.
van’t Hoff Factor
Colligative Properties Measure of the extent to which electrolytes dissociate
Changes in colligative properties depend only on the Ratio of the actual value of a colligative property to the
number of solute particles present, not on the identity of value calculated assuming the substance to be a
the solute particles. nonelectrolyte
Among colligative properties are We modify the previous equations by multiplying by
-Vapor pressure depression the van’t Hoff factor, i
-Boiling point elevation
-Freezing point depression DTf = Kf ž m ž i or DTb = Kb ž m ž i
-Osmotic pressure
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, p, is

n
p=i( )RT = iMRT
V

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 CCl 4
elevates the boiling point by 0.49 °C. Calculate the
approximate molar mass of adrenaline from this data.

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