Liquids and Intermolecular Forces melting points, viscosity, surface tension,

States of Matter and capillary action.

➢ The fundamental difference between Types of Intermolecular Force
states of matter is the strength of the Weakest to strongest forces:
intermolecular forces of attraction. ➢ dispersion forces (or London dispersion
➢ Stronger forces bring molecules closer forces)
together. ➢ dipole–dipole forces
➢ Solids and liquids are referred to as the ➢ hydrogen bonding (a special
condensed phases. dipole–dipole force)
➢ ion–dipole forces
Which State of Matter?
The answer to this question largely relies on Note: The first two types are also referred to
collectively as van der Waals forces.
the:
➢ balance between the kinetic energies of Dispersion Forces
the particles.
➢ interparticle energies of attraction.

➢ The figure shows how a nonpolar particle

(in this case a helium atom) can be
temporarily polarized to allow dispersion
force to form.
➢ The tendency of an electron cloud to
distort is called its polarizability.
Intermolecular Forces
Factors Which Affect Amount of Dispersion
Force in a Molecule

➢ The attractions between molecules are

not nearly as strong as the intramolecular
attractions (bonds) that hold compounds
together.
➢ number of electrons in an atom (more
➢ Many physical properties reflect
electrons, more dispersion force)
intermolecular forces, like boiling points,
➢ size of atom or molecule/molecular weight
 ➢ shape of molecules with similar masses
(more compact, less dispersion force)
Polarizability & Boiling Point
➢ If something is easier to polarize, it has a
lower boiling point.
➢ Remember: This means
intermolecular force (smaller molecule:
lower molecular weight, fewer electrons).
Dipole–Dipole Interactions
Which Have a Greater Effect: Dipole–Dipole
Interactions or Dispersion Forces?
➢ If two molecules are of comparable size
and shape, dipole–dipole interactions will
likely be the dominating force.
➢ If one molecule is much larger than
another, dispersion forces will likely
determine its physical properties.
Hydrogen Bonding
➢ The dipole–dipole
interactions experienced
when H is bonded to N,
O, or F are unusually
strong.
➢ We call these
interactions hydrogen
bonds.
less ➢ A hydrogen bond is
an attraction between a
hydrogen atom attached
to a highly
electronegative atom and
a nearby small
electronegative atom in
another molecule or chemical group.
What Forms Hydrogen Bonds?

➢ Polar molecules have a more positive and

a more negative end–a dipole (two poles,
δ+ and δ−). ➢ Hydrogen bonding arises in part from the
➢ The oppositely charged ends attract each high electronegativity of nitrogen, oxygen,
other. and fluorine.
➢ These atoms interact with a nearly bare
nucleus (which contains one proton).
Ion–Dipole Interactions

➢ For molecules of approximately equal

mass and size, the more polar the
molecule, the higher its boiling point.
 ➢ Ion–dipole interactions are found in
solutions of ions.
➢ The strength of these forces is what
makes it possible for ionic substances to
dissolve in polar solvents.
Summarizing Intermolecular Forces

Liquid Properties Affected by Intermolecular

Forces
Cohesion and Adhesion
➢ boiling point (previously discussed) and
➢ Intermolecular forces that bind similar
melting point
molecules to one another are called
➢ viscosity
cohesive forces.
➢ surface tension
➢ Intermolecular forces that bind a
➢ capillary action
substance to a surface are called
Viscosity adhesive forces.
➢ Resistance of a ➢ These forces are important in capillary
liquid to flow is called action.
viscosity.
Capillary Action
➢ It is related to the
ease with which
molecules can move
past each other.
➢ Viscosity
increases with stronger
intermolecular forces
and decreases with
higher temperature.
Surface Tension
➢ Water acts as if it has a “skin” on it due to
extra inward forces on its surface. Those
forces are called the surface tension.
 ➢ The rise of liquids up narrow tubes is
called capillary action.
➢ Adhesive forces attract the liquid to the
wall of the tube.
➢ Cohesive forces attract the liquid to itself.
➢ Water has stronger adhesive forces with
glass; mercury has stronger cohesive
Heating Curves
forces with itself.
Phase Changes
➢ Conversion from one state of matter to
another is called a phase change.
➢ Energy is either added or released in a
phase change.
➢ Phase changes: melting/freezing,
vaporizing/condensing,
subliming/depositing.
Energy Change & Change of State
Supercritical Fluids
➢ The heat of fusion is the energy required
to change a solid at its melting point to a
liquid.
➢ The heat of vaporization is the energy
required to change a liquid at its boiling
point to a gas.
➢ The heat of sublimation is the energy
required to change a solid directly to a
gas.
➢ A plot of temperature vs. heat added is
called a heating curve.
➢ Within a phase, heat is the product of
specific heat, sample mass, and
temperature change.
➢ The temperature of the substance does
not rise during a phase change.
➢ For the phase changes, the product of
mass and the heat of fusion of
vaporization is heat.
➢ Gasses liquefies when pressure is
applied.
 ➢ The temperature beyond which a gas
cannot be compressed is called its
critical temperature.
The pressure needed to compress the
liquid at critical temperature is
called critical pressure.
➢ The state beyond this temperature is
called a supercritical fluid.
Vapor Pressure

➢ The boiling point of a liquid is the

temperature at which its vapor pressure
equals atmospheric pressure.
➢ The normal boiling point is the
temperature at which its vapor pressure is
760 torr.

➢ At any temperature, some liquid

molecules have enough energy to escape
the surface and become a gas.
➢ As the temperature rises, the fraction of
molecules that have enough energy to
break free increases.

➢ The natural log of the vapor pressure of a

liquid is inversely proportional to its
temperature.
➢ This relationship is quantified in the
➢ As more molecules escape the liquid, the Clausius–Clapeyron equation.
pressure they exert increases.
➢ The liquid and vapor reach a state of
dynamic equilibrium: liquid molecules
evaporate and vapor molecules condense
at the same rate.
Phase Diagram
➢ A phase diagram is a graph of pressure
vs. temperature for a substance. It shows:
- melting, boiling, and sublimation points
at different pressures.
- the triple point and critical point.

Phase Diagram of Water

➢ Note the high critical temperature and Liquid Crystals
critical pressure.
- These are due to the strong van der
Waals forces between water molecules.

➢ Some substances do not go directly from

the solid state to the liquid state.
➢ In this intermediate state, liquid crystals
have some traits of solids and some of
liquids.
➢ Molecules in liquid crystals have some
degree of order.
Unusual feature for water:
➢ The slope of the solid – liquid line is
negative.
➢ This means that as the pressure is
increased, the melting point decreases.
Phase Diagram of Carbon Dioxide
Unusual features for carbon dioxide:
➢ cannot exist in the liquid state at
➢ In nematic liquid crystals, molecules are
pressures below 5.11 atm (triple point)
only ordered in one dimension, along the
➢ CO2 sublimes at normal pressures.
long axis.
➢ In smectic liquid crystals, molecules are
ordered in two dimensions, along the long
axis and in layers.
 ➢ In cholesteryic liquid crystals, ➢ Triple Point: A unique temperature and
nematic-like crystals are layered at angles pressure at which three phases (usually
to each other. solid, liquid, and gas) can exist together.
➢ Critical Point: The temperature and
Temperature
pressure at which gas and liquid merge
➢ A measure of the average kinetic energy
together to form a supercritical fluid.
(energy of motion) of particles (atoms or
Beyond this temperature, no amount of
molecules) in matter in Celsius, Kelvin, or
pressure will condense the gas to a liquid.
Fahrenheit.
➢ Normal Melting Point – At 1 atm
Pressure pressure, the temperature at which the
➢ A measure of how tightly matter is solid melts to liquid.
squeezed together in units of ➢ Normal Boiling Point – At 1 atm
atmospheres (atm), bars, torrs, Pascals pressure, the temperature at which the
(Pa) or even pounds/in2 (psi). liquid vaporizes to become a gas.
Phase Diagram of Carbon In general,
➢ High pressures favor liquids and
solids because the atoms are packed
closer together (more dense).
➢ Low pressures and high temperatures
favor gases (less dense).
➢ High temperatures favor liquids and
gases because the atoms are less tightly
packed, and are more mobile and
energetic.
The H2O Phase Diagram

Phase Diagram for Carbon Dioxide (CO2)

➢ In a 1 phase field, only one state is

possible.
➢ On a phase boundary, two states will
coexist.
➢ At a triple point, three states coexist.
Solution Concentration
➢ A solution is a homogeneous mixture.
➢ The solvent is the major component of the
solution.
➢ The solute is the minor component and
active ingredient.
➢ A saturated solution holds the maximum
amount of solute that is theoretically
possible for a given temperature.
Concentration
➢ A ratio comparing the amount of solute to
the amount of solution.
➢ Many ways of expressing concentration:
Molarity (M) is the one we will be dealing
with.
Concentrated vs. Dilute
➢ The words “concentrated” and “dilute” are
opposites.
Example:
- The dark tea is more concentrated
than the light tea.
- The light tea is more dilute than the
dark tea.
Molarity
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑀) = 𝐿𝑖𝑡𝑒𝑟𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
➢ Units: mol/L or Molar (M)
Example:
- What is the Molar concentration of a
sol’n if 20.0 grams of KNO3 (MM =
101.11 g/mol) is dissolved in enough
water to make 800. mL?
Solution:
Dilution
➢ To add solvent to a solution.
➢ Decreases solution concentration.
➢ M1V1 = M2V2
- M1 = initial conc.
- V1 = initial volume
- M2 = final conc.
- V2 = final volume
➢ Assumes no solute is added.
Conductivity
➢ Pure water does not conduct electricity
- Some solutions do
➢ In order to conduct a current, a solution
must contain ions
➢ Conductivity depends on the nature of the
particle
- Molecular solutes do not conduct
Colligative Properties
➢ A property that depends only upon the
number of solute particles (concentration),
and NOT upon their identity.
➢ Depend on the number of particles in
solution not on the type of particles
- Doesn’t matter what kind of particles:
can be ions or molecules
- Concentration of particles does
matter
What are some colligative properties?
➢ Vapor Pressure Lowering
➢ Freezing Point Depression
➢ Boiling Point Elevation
➢ change in Osmotic Pressure
 - The higher the concentration of solute
particles, the larger the effect
Does it matter if the solute is ionic or covalent?
➢ number of particles will vary
➢ Ionic solutes
- dissolve to produce (+) & (-) ions
more particles per mole of solute
➢ Covalent solutes
- 1-to-1 relationship between moles of
solute and moles of dissolved
particles
Vapor-Pressure Lowering
➢ Vapor pressure is the pressure exerted by
a vapor that is in dynamic equilibrium with
its liquid (molecules are moving back and
forth between liquid and vapor phases).
➢ A solution that contains a solute that is
not easily vaporized always has a lower
vapor pressure than the pure solvent.
➢ This is true because in a solution, solute
particles reduce the number of free
solvent particles able to escape the liquid.
➢ The decrease in a solution’s vapor
pressure is proportional to the number of
particles the solute makes in solution.
Freezing-Point Depression
➢ The difference in temperature between
the freezing point of a solution and the
freezing point of the pure solvent (water).
➢ The presence of a solute in water disrupts
the formation of the orderly pattern of ice.
Therefore more kinetic energy must be
withdrawn from a solution than from the
pure solvent to cause the solution to
solidify.
➢ The magnitude of the freezing-point
depression is proportional to the number
of solute particles dissolved in the solvent
and does not depend upon their identity.
Boiling-Point Elevation
➢ The temperature at which the vapor
pressure of the liquid phase equals
atmospheric pressure.
➢ Because of the decrease in vapor
pressure, additional kinetic energy must
be added to raise the vapor pressure of
the liquid phase of the solution to
atmospheric pressure to initiate boiling.
➢ The difference in temperature between
the boiling point of a solution and the
boiling point of the pure solvent.
➢ The boiling point of a solution is higher
than the boiling point of the pure solvent.
➢ The magnitude of the boiling-point
elevation is proportional to the number of
solute particles dissolved in the solvent.
➢ It takes additional kinetic energy for the
solvent particles to overcome the
attractive forces that keep them in the
liquid.
➢ The water molecules are attracted to ions
in solution, the ions “hold” the water
molecules down instead of allowing them
to be released into the vapor phase. The
water molecules need more energy to
“escape” from the ions in solution!
Applications of Colligative Properties
➢ Salting roads in the winter time
➢ Using salted ice to make ice cream
Chemical Kinetics
➢ Chemical kinetics is the study of the
speed or rate of a reaction under various
conditions.
➢ Spontaneity is also important AND a
spontaneous reaction does NOT imply a
rapid reaction.
➢ The changing of diamond into graphite is
spontaneous but so slow that it is not
detectable even in a lifetime.
➢ A mechanism is a sequence of events at
the molecular level that controls the
speed and outcome of the reaction.
Factors that Affect Reaction Rates
1) Nature of the reactants
- Some reactant molecules react in a
hurry, others react very slowly.
Chemical identity: What is reacting?
- Usually, ions of opposite charge react
very rapidly.
- Usually, the more bonds between
reacting atoms in a molecule, the
slower the reaction rate.
 - Substances with strong bonds (larger ➢ Proper orientation of colliding molecules
bond energies) will react much more so that atoms can come in contact with
slowly. each other to become products.
2) Concentration of reactants ➢ The collision must occur with enough
- More molecules, more collisions. energy to overcome the electron/electron
3) Temperature repulsion of the valence shell electrons of
- The faster they move, the more likely the reacting species and must have
they are to collide. enough energy to transform translational
- An increase in temperature produces energy into vibrational energy in order to
more successful collisions that are penetrate into each other so that the
able to overcome the needed electrons can rearrange and form new
activation energy, therefore, a general bonds.
increase in reaction rate with ➢ This new collision product is at the peak
increasing temperature. of the activation energy hump and is
4) Catalysts called the activated complex or the
- Accelerate chemical reactions but are transition state. At this point, the
not themselves transformed. activated complex can still either fall to
- Biological catalysts are proteins reactants or to products.
called enzymes.
- A catalyst is a substance that
changes the rate of reaction by
altering the reaction pathway.
- Most catalysts work by lowering the
activation energy needed for the
reaction to proceed; therefore, more
collisions are successful and the
reaction rate is increased.
- Remember! The catalyst is not part of
the chemical reaction and is not used
up during the reaction.
- A catalyst lowers the activation
energy barrier. Therefore, the
forward and reverse reactions are
both accelerated to the same degree.
5) Surface area of reactants
- Exposed surfaces affect speed.
- Except for substances in the gaseous
state or solution, reactions occur at
the boundary, or interface, between
two phases.
- The greater surface area exposed,
the greater chance of collisions
between particles, hence, the reaction
should proceed at a much faster rate.
The Collision Theory of Reaction Rates
➢ Particles must collide.
➢ Only two particles may collide at one time.
Thermodynamics
➢ The study of the movement of thermal
energy (heat).
Thermodynamic Systems
➢ A thermodynamic system is a specific
portion of matter with a definite boundary
on which our attention is focused. The
system boundary may be real or
imaginary, fixed or deformable.
➢ Isolated System – An isolated system
cannot exchange energy and mass with
its surroundings. The universe is
considered an isolated system.
➢ Closed System – Across the boundary of
the closed system, the transfer of energy
takes place but the transfer of mass
doesn’t take place. Refrigerator
compression of gas in the piston-cylinder
assembly are examples of closed
systems.
➢ Open System – In an open system, the
mass and energy both may be transferred
between the system and surroundings. A
steam turbine is an example of an open
system.
Thermodynamic Equilibrium
➢ When the temperature is the same
throughout the entire system, we consider
the system to be in thermal equilibrium.
➢ When there is no change in pressure at
any point of the system, we consider the
system to be in mechanical equilibrium.
➢ When the chemical composition of a
system does not vary with time, we
consider the system to be in chemical
equilibrium.
➢ Phase equilibrium in a two-phase
system is when the mass of each phase
reaches an equilibrium level.
Thermodynamic Properties
➢ Exothermic process is any process that
gives off heat – transfers thermal energy
from the system to the surroundings.
Processes in which energy is released as
it proceeds, and surroundings become
warmer.
➢ Endothermic process is any process in
which heat has to be supplied to the
system from the surroundings. Processes
in which energy is absorbed as it
proceeds, and surroundings become
colder.
Types of Heat Transfer
➢ Radiation – The transfer of energy by
electromagnetic waves.
➢ Convection – Transfer of energy by
currents
➢ Conduction – Transfer of energy by
touching objects
Laws of Thermodynamics
1st Law
➢ The first law of thermodynamics is a
statement of the law of conservation of
energy: “Energy can be neither created
nor destroyed. In other words, the energy
of the universe is constant.”
2nd Law
➢ “In any spontaneous process there is
always an increase in the entropy of the
universe.”
➢ “The entropy of the universe is
increasing.”
➢ For a given change to be spontaneous,
∆Suniverse must be positive
∆Suniv = ∆Ssys + ∆Ssurr
3rd Law
➢ “The entropy of a perfect crystal at 0 K is
zero’ (NO disorder, since everything is in
perfect position)
➢ No movement = 0 K
➢ No disorder = no entropy (DS = 0)
Energy in Chemical Reactions
A + B → C + D + Energy
➢ The potential energy is broken in
chemical bonds in compounds A and B.
➢ The potential energy of the chemical
bonds of C and D is lower.
➢ The excess has been given off (energy)
as thermal energy, or heat, which is
kinetic energy transferred to the
surroundings.
Spontaneity
➢ Spontaneous Processes - Processes that
occur without outside intervention
➢ Spontaneous processes may be fast or
slow
- Many forms of combustion are fast
- Conversion of graphite to diamond is
slow
- Kinetics is concerned with speed,
thermodynamics with the initial and
final state
➢ Spontaneity can change when the
temperature changes.
➢ Temperature and spontaneity are not
necessarily correlated.
- A reaction with a negative entropy
(loss of randomness) would be LESS
spontaneous at higher temperatures
– it doesn’t want to happen, but is
pushed by the extra heat.
Entropy (S)
➢ Entropy is a thermodynamic quantity
whose value depends on the physical
state or condition of a system. In other
words, it is a thermodynamic function
used to measure the randomness or
disorder.
➢ A measure of randomness or disorder.
➢ The driving force for a spontaneous
process is an increase in the entropy of
the universe (one of the laws of
thermodynamics).
➢ Entropy is a thermodynamic function
describing the number of arrangements
that are available to a system.
➢ Nature proceeds towards the states that
have the highest probabilities of existing.
Positional Entropy
➢ The probability of occurrence of a
particular state depends on the number of
ways (microstates) in which that
arrangement can be achieved
∆Ssolid < ∆Sliquid << ∆Sgas
Entropy and Temperature
➢ Entropy changes in the surroundings are
primarily determined by heat flow.
➢ The magnitude of entropy is dependent
on the temperature.
➢ The lower the temperature, the higher the
impact to the surroundings of the transfer
of energy.
Entropy and Exothermic Processes
➢ Entropy and a process being exothermic
are related, but a process doesn’t have to
be both.
➢ Exothermic process
- ∆Ssurr = positive, exothermic = more
disorder in surroundings
➢ Endothermic process
- ∆Ssurr = negative, endothermic = less
disorder in surroundings
- ∆Ssystem must increase to obey 2nd
Law of Thermodynamics
More on Entropy
➢ Why is the sign different?
- The enthalpy (H) concerns the
system
- Our entropy here concerns the
surroundings
- As usual, temperatures must be in
Kelvin
Free Energy (G)
∆G = ∆H - T∆S
➢ Typically defined as the energy available
to perform work.
➢ G determines whether a process is
spontaneous or not (∆G = negative =
spontaneous).
- Takes into account enthalpy, entropy,
and temperature.
- Symbol honors Josiah Gibbs
(sometimes called Gibbs Free Energy
or Gibbs energy), a physics professor
at Yale during the late 1800’s who
was important in developing much of
modern thermodynamics.
➢ Free energy (G) values tell us if reactions
will occur.
Energy Diagrams
➢ Left – A spontaneous reaction
- The products have a lower free
energy (G) than the reactants (DG <
0)
➢ Right – A nonspontaneous reaction
- The reactants have a higher free
energy than the products (DG > 0)
Entropy Changes in Chemical Reactions
➢ Constant Temperature and Pressure –
Reactions involving gaseous molecules
- The change in positional entropy is
dominated by the relative numbers of
molecules of gaseous reactants and
products.
Calculating Entropy Change in a Reaction
➢ Calculates standard entropy of a reaction,
uses standard entropies of compounds.
➢ Entropy is an extensive property (a
function of the number of moles).
➢ Generally, the more complex the
molecule, the higher the standard entropy
value.
Calculating Free Energy of Formation
Free Energy and Work
➢ The maximum possible useful work
obtainable from a process at constant
temperature and pressure is equal to the
change in free energy
➢ The amount of work obtained is always
less the maximum
- Work is changed to heat in
surroundings – You lose efficiency,
but the ∆Ssurr increases (favorable).
➢ Henry’s Bent’s First Two Laws of
Thermodynamics
- 1st Law: You can’t win, you can only
break even.
- 2nd Law: You can’t break even.
Enthalpy
➢ Enthalpy is the measurement of energy in
a thermodynamic system. The quantity of
enthalpy equals the total heat content of a
system, equivalent to the system’s
internal energy plus the product of volume
and pressure.
Thermochemistry
➢ Deals with the changes in energy that
accompany a chemical reaction. Energy
is measured in a quantity called enthalpy,
represented as ∆H. The change in
energy that accompanies a chemical
reaction is represented as ∆H.
➢ In thermochemical equations the quantity
of energy released or absorbed as heat
during a reaction is written and is
represented by ∆H.
➢ ∆H can be used to determine if the
reaction is exothermic or endothermic. If
the ∆H value of an equation is negative
that represents an exothermic reaction.
(Meaning energy is released, therefore
the energy of the products would be less.)
➢ If the ∆H value of an equation is positive
that represents an endothermic reaction.
➢ Hess’s law provides a method for
calculating the ∆H of a reaction from
tabulated data. This law states that if two
or more chemical equations are added,
the ∆H of the individual equations may
also be added to find the ∆H of the final
equation. As an example of how this law
operates, look at the three reactions
below.
Calorimeter ➢ Static equilibrium is a state in which no
movement occurs.
➢ Dynamic equilibrium, two opposing
processes are occurring simultaneously
with no net charge.
➢ A reversible reaction occurs when
reactants can form products (the forward
reaction) and then the products can come
apart to form the reactants (the reverse
reaction).

➢ The energy absorbed or released as heat

in a chemical or physical change is
measured in a calorimeter. In one kind of
calorimeter, known quantities of reactants Activation Energy
are sealed in a reaction chamber, which is
immersed in a known quantity of water in
an insulated vessel. Therefore, the
energy given off (or absorbed) during the
reaction is equal to the energy absorbed
(or given off) by the known quantity of
water. The amount of energy is
determined from the temperature change
of the known mass of surrounding water.
➢ Using the change in temperature, ∆T,
determined from calorimeter one can use
the following equation to determine the
quantity of energy gained or lost during
the reaction or for a physical change:
q = (cp)(m)(∆T)
∆T in kelvin
q represents the energy lost or gained (J)
m is the mass of the sample (g)
cp is the specific heat of a substance at a
given temperature ➢ The forward reaction will go faster than
Equilibrium the reverse reaction since it takes less
➢ Equilibrium is a condition in which all energy to activate.
influences are canceled by other
influences, resulting in a stable, balanced
or unchanging system.
Equilibrium Constant
➢ The equilibrium constant is the ratio of the
concentrations of products divided by the
concentrations of reactants. The
equilibrium constant tells us information
about the extent and efficiency of the
reaction.
➢ Having knowledge about the equilibrium
constant will allow a chemical factory
employee to maximize products through
adjusting conditions such as
concentration, temperature, and pressure.
Equation for the equilibrium constant for a
reaction:
𝑐 𝑑
[𝐶] [𝐷]
𝐾𝑒𝑞 = 𝑎 𝑏
[𝐴] [𝐵]
➢ Reactants are placed in the denominator
(A and B on the bottom), while products
are placed in the numerator (C and D on
top).
➢ At equilibrium, the rate of the forward and
reverse reaction are equal.
➢ When equilibrium is reached, the
concentration of reactants remains the
same and the concentration of products
remains the same.
➢ The value of 𝐾𝑒𝑞 indicates whether a
chemical reaction favors the formation of
products (𝐾𝑒𝑞>1), reactants (𝐾𝑒𝑞<1), or
proceeds to a moderate extent in both
directions (𝐾𝑒𝑞 ≈ 1) at equilibrium.
Le Chatelier's Principle
➢ Le Chatelier’s principle states that if a
system at equilibrium is subjected to a
change, it will adjust to counteract that
change and restore equilibrium. When
equilibrium is stressed, the system
adjusts to reestablish equilibrium.
➢ Chemical equilibrium can be stressed by
changes in concentrations of reactants
or products, pressure (for reactions
involving gases), and temperature.
Changes in temperature are the only one
among the listed ways that can cause the
equilibrium constant (Keq) of the reaction
to change.
➢ This principle helps us predict how
chemical reactions respond to external
influences.
The Haber Process
➢ An increase in pressure or a decrease in
volume in the system will result in
production of more ammonia.
➢ Removal of ammonia (product) during the
reaction causes the equilibrium to shift to
the right, thereby making more ammonia.
Remember:
➢ If you add more reactants, the reaction
will shift right, towards products.
➢ If you add more products, the reaction will
shift left, towards reactants.
➢ If you take away product, the reaction will
shift right to more product.
➢ If you take away the reactant, the reaction
will shift left to make more reactants.
Acid and Base Equilibrium
History of Acids and Bases
➢ In the early days of chemistry chemists
were organizing physical and chemical
properties of substances. They
discovered that many substances could
be placed in two different property
categories:
Substance A (Acid)
Sour taste
Reacts with carbonates to make CO2
Reacts with metals to produce H2
Turns blue litmus pink
 Reacts with base to make salt and
water
Substance B (Base)
Bitter taste
Reacts with fats to make soaps
Do not react with metals
Turns red litmus blue
Reacts with acid to make salt and water
➢ In 1909, Søren Peter Lauritz Sørensen,
a Danish chemist, developed a method of
quantifying acidity now known as the pH
Scale. The scale works by converting H+
ion concentrations in a solution to a value
between 0-14. If a chemical is acidic,
then its pH will always be below a 7 on
the scale. The lower the number, the
higher the H+ concentration. Substances
that fall between 8-14 are called bases. 7
is neutral pH, perfectly pure water.
➢ Antoine Lavoisier thought that acidity
came from oxygen atoms and molecules.
From the Greek words “oxys” (meaning
sharp) and “genes” (meaning something
that produces), oxygen was something
that produces sharp to Lavoisier.
The Arrhenius Theory of Acids and Bases
➢ First definition of acids and bases: The
Swedish chemist Svante Arrhenius
proposed a theory to explain the
characteristic properties of acids &
bases. The characteristic properties of
acids are due to the formation of
hydrogen ions, while the characteristic
properties of bases are due to the
presence of hydroxide ions.
➢ The Arrhenius definition for acids and
bases only refers to compounds
dissolved in water.
“Acids are substances that dissociate in water
to produce H+ ions and bases are substances
that dissociate in water to produce OH- ions.”
➢ Arrhenius acids: a substance that
contains hydrogen and ionizes to produce
hydrogen ions, H+, in aqueous solution.
+ −
𝐻𝐶𝑙 (𝑎𝑞) → 𝐻 + 𝐶𝑙
(𝑎𝑞) (𝑎𝑞)
➢ Arrhenius bases: a substance that
contains a hydroxide group and
dissociates to produce a hydroxide ion,
OH-, in aqueous solution.
+ −
𝑁𝑎𝑂𝐻 (𝑎𝑞) → 𝑁𝑎 (𝑎𝑞)
+ 𝑂𝐻 (𝑎𝑞)
Characteristics of Acids and Bases
Physical Properties
➢ Acidic solutions taste sour
- Carbonic and phosphoric acid give
carbonated beverages a sharp taste
- Acetic acid makes vinegar a sour
taste
- Citric and ascorbic acids give lemons
and grapefruits their tartness
➢ Basic solutions taste bitter and are
slippery
➢ Both can conduct electricity due to freely
moving ions in solution (aka electrolytes)
➢ The greater the concentration of ions in
solution, the stronger the electrolyte
- Strong acids and bases = strong
electrolytes
- Weak acids and bases = weak
electrolytes
Chemical Properties
➢ Aqueous solutions of acids react with
active metals (those above hydrogen on
Table J) to produce hydrogen gas
➢ Aqueous solutions of acids and bases
change the color of acid-base indicators
(Table M)
➢ Acids and bases react together to form
water and salt (this is a neutralization
reaction).
Bronsted-Lowry Theory
➢ Johannes Brønsted and Thomas Lowry
revised Arrhenius’s acid-base theory to
include other solvents besides water.They
defined acids and bases as follows:
“An acid is a hydrogen containing species that
donates a proton. A base is any substance that
accepts a proton”
− +
𝐻𝐶𝑙 (𝑎𝑞) + 𝐻2𝑂 (𝑙) → 𝐶𝑙 (𝑎𝑞)
+ 𝐻3𝑂
➢ The reaction of HCl with H2O is an
equilibrium and occurs in both directions,
although in this case the equilibrium lies
far to the right.
➢ For the reverse reaction Cl - behaves as a
Brønsted base and H3O+ behaves as a
Brønsted acid. The Cl- is called the
conjugate base of HCl.
➢ Bronsted-Lowry acid: Any compound
that can donate a proton (H+) ion to
another compound; donates protons.
➢ Bronsted-Lowry base: Any compound
that can accept a proton from another
compound; accepts protons.
➢ Brønsted acids and bases always exist as
conjugate acid-base pairs. Their formulas
differ by only one proton.
➢ A single arrow is used to represent the
ionization of strong acids.
+ −
𝐻𝐶𝑙 (𝑔) → 𝐻 (𝑎𝑞)
+ 𝐶𝑙
➢ Double arrows are used to represent
ionization of weak acids because an
equilibrium is created.
+ −
𝐻𝐹 (𝑔) ⇆ 𝐻 +𝐹
(𝑎𝑞) (𝑎𝑞)
Autoionization of Water
➢ In pure water (no solute) water molecules
behave as both an acid and base. It is
called amphoteric meaning it will act as
either an acid or a base depending on the
situation.
𝐻2𝑂 (𝑙) + 𝐻2𝑂 (𝑙) → 𝐻3𝑂
+ −
+ 𝑂𝐻
(𝑎𝑞)
(𝑎𝑞)
(𝑎𝑞) ➢ This is called the autoionization of water.
Although the equilibrium lies far to the left
it is very important to take into
consideration, especially for living
systems.
➢ For pure water [OH-] = [H+].
➢ Kw is called the ionization constant of
water and is very small. As with all Kw
values, it is temperature dependent.
➢ This only means that the neutral value for
pH is getting lower, it does not mean that
the solution is becoming more acidic as
the temperature increases.
➢ We define an aqueous solution as being:
- neutral when [H+] = [OH-]
- acidic when [H+] > [OH-]
- basic when [H+] < [OH-]
pH Calculations
pH = -log [H+]
(𝑎𝑞)
pOH = -log [OH-]
pH + pOH = 14 for water solutions
Calculations for Molarity Concentrations
−𝑝𝐻
𝑀 = 2𝑛𝑑 𝑙𝑜𝑔 = 10
−𝑝𝑂𝐻
𝑀 = 2𝑛𝑑 𝑙𝑜𝑔 = 10
➢ The number of decimal places in the log
answer is equal to the number of sig figs
in the original Molar [ ].
 ➢ Weak base has Kb < 1
➢ Leads to small [OH-] and a pH of 12-7.
Calculating the pH of Weak Acid Solutions
𝑎𝑚𝑜𝑢𝑛𝑡 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 (𝑚𝑜𝑙/𝐿)
% 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 = 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝑚𝑜𝑙/𝐿)
× 100
+
[𝐻 ]
%𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 = [𝐻𝐴]
× 100
➢ In general, if the percent dissociation is
less than or equal to 5%, then it is
completely acceptable to ignore the X
value in the ice table.
➢ The justification for this is that Ka and Kb
values are typically known only to an
accuracy of ±5%.

Acid and Base Equilibrium

➢ Strong acids and strong bases completely
dissociate in water. Therefore they DO
NOT create an equilibrium system.
➢ Weak acids and weak bases dissociate to
a far lesser degree in an aqueous
solution. They DO create an equilibrium
system .
➢ They have their own Kc constants.
➢ K is designated Ka acid dissociation
constant.
➢ K gives the ratio of ions to molecules.
➢ Pure substances are not shown in the Ka
constant.
➢ The greater the dissociation, the larger
the Ka will be.
Equilibrium Constants for Weak Acids

➢ Weak acid has Ka < 1

➢ Leads to small [H3O+] and a pH of 2-7.
Equilibrium Constants for Weak Bases