Chemistry

Engr. Edgie L.
Estopace
B.S Chemical Engineering
B.S Chemistry
• Introduction to Gases : Air
Pollution
• Properties of Gases
• Gas Laws
• Kinetic- Molecular Theory for
Gases
• Ideal and Real Gases
• Stoichiometry of Reactions
Air Pollution
 Clean air is a mixture of
several gases.
 Nitrogen and oxygen

are major components
 Water vapor
(humidity) varies with
place, time, and
temperature.
 Dry air is a convenient

reference point
Air Pollution
 Six Principal Criteria Pollutants
 CO, NO2, O3, SO2, Pb, and Particulate Matter (PM)
 Commonly found throughout the country; cause a variety of

negative effects on health, environment, and/or property.
Air Pollution
 The criteria pollutant nitrogen dioxide, NO2, is
emitted by automobiles.
 High temperatures inside car engines cause oxygen

and nitrogen to react to produce a variety of
nitrogen oxides, designated with the generic
formula NOx.
 Brown color of smog due to NO2; attacks lung

membranes
Air Pollution
 Photochemical reactions, reactions initiated by light
energy, can trigger formation of ozone, another criteria
pollutant, at ground level from:
 volatile organic compounds (VOCs): hydrocarbons
that readily evaporate
 Reactions between these two types of compounds
produce a mixture a gases collectively referred to as
smog.
 Many components are lung irritants.
 Ozone is the most significant lung irritant.
States of Matter: Looking back
 Solids
7
States of Matter
 Solids
 Liquids
8
States of Matter
 Solids
 Liquids
 Gases
9
Properties of Gases
 Expand to fill the volume of any container.
 Have much lower densities than solids or liquids.
 Have highly variable densities, depending on

conditions.
 Mix with one another readily and thoroughly.
 Change volume dramatically with changing

temperature.
Properties of Gases
 The ideal gas law is the quantitative relationship between
pressure (P), volume (V), moles gas present (n), and the
absolute temperature (T).
 R is the universal gas constant.

 R = 0.08206 L atm mol-1 K-1: used in most gas equations
 R = 8.314 J mol-1 K-1 : used in equations involving energy
PV nRT
Pressure P
F
A
 Pressure is force per unit area.
 Atmospheric pressure is the force attributed to the

weight of air molecules attracted to Earth by gravity.
 As altitude increases, atmospheric pressure decreases.

Pressure
 Pressure results from
molecular collisions
between gas molecules
and container walls.
 Each collision imparts a

small amount of force.
 Summation of the
forces of all molecular
collisions produces the
macroscopic property
of pressure.
Measuring Pressure
 A barometer is used to measure
atmospheric pressure.
 The height of the mercury

column is proportional to
atmospheric pressure.
 Units of Pressure
 1 torr = 1 mm Hg
 1 atm = 760 torr (exactly)
 1 atm = 101,325 Pa (exactly)
 760 torr = 101,325 Pa (exactly)
History and Application of the Gas Law
 Gases change significantly when the conditions in
which they are found are altered.
 These changes are determined empirically using gas

laws.
 Charles’s Law: relationship between T and V

 Boyle’s Law: relationship between P and V
 Avogadro’s Law: relationship between n and V
 The empirical gas laws led to the ideal gas law

Charles’s Law
 Jacques Charles studied relationship between volume
and temperature.
 Plots of V versus T for different gas samples converged to

the same temperature at zero volume.
 Basis of the Kelvin temperature scale.
Charles’s Law
 For fixed pressure and fixed number of moles of gas,
the volume and the absolute temperature of a gas are
directly proportional.
V T
 All of the fixed variables can be factored out of the
ideal gas law as a new constant that can be used to
relate two sets of conditions:
V1 nR V2
constant
T1 P T2
Boyle’s Law
 Pressure and volume are inversely proportional.
1
V
P
 All of the fixed variables can be factored out as a new

constant that can be used to relate two sets of
conditions:
P1V1 nRT constant P2V2
Avogadro’s Law
 Avogadro’s Law states that for fixed pressure and
temperature, the volume and moles of a gas are
directly proportional.
V n
V1 RT V2
constant
n1 P n2
Example Problem 5.1
 A common laboratory cylinder of methane has a
volume of 49.0 L and is filled to a pressure of 154 atm.
Suppose that all of the CH4 from this cylinder is
released and expands until its pressure falls to 1.00
atm. What volume would the CH4 occupy?
Example Problem 5.2
 A balloon is filled with helium and its volume is 2.2 L
at 298 K. The balloon is then dunked into a thermos
bottle containing liquid nitrogen. When the helium in
the balloon has cooled to the temperature of the liquid
nitrogen (77 K), what will the volume of the balloon
be?
Units and the Ideal Gas Law
 Temperature must be expressed in Kelvin for all gas calculations!
 Negative temperatures would result in negative pressures,
volumes, and moles.
 In some engineering fields, the Rankine temperature scale is
used, which is another absolute temperature scale.
 0˚R = 0 K; 1˚R = 1.8 K
 The unit for moles is always mol.
 The units for measuring pressure and volume can vary. In gas
calculations, these units must agree with those of the gas
constant
 R = 8.314 J mol-1 K-1
 R = 0.08206 L atm mol-1 K-1
 R = 62.37 L torr mol-1 K-1
Example Problem 5.3
 A sample of CO2 gas has a volume of 575 cm3 at 752
torr and 72˚F. What is the mass of carbon dioxide in
this sample?
Molar Mass and Density
 Density = mass/volume
 Recall that the molar mass has units of grams (mass)
per mole
 Now, look at the ideal gas law:
 The number of moles appears
 Moles, n, can be expressed as mass/MM
 There is also a volume term in the ideal gas law
Rewriting the Ideal Gas Law in Density Terms
m
PV RT
MM
m P MM
d
V R T
Density of Gases
 Density is an extensive property
 Does not depend on the amount of substance
 Density of a gas does depend on
 Pressure
 Temperature
 Molar mass
Example 5.4
Example 5.4 (cont'd)
 The Gas Laws
BOYLE’S LAW
 If the temperature remains constant, the volume of a given mass
of gas varies inversely with the pressure.
CHARLES’ LAW
 If the pressure does not change, the volume of a given mass of
gas is directly proportional to the absolute temperature.
AVOGADRO’S LAW
 Equal number of molecules are contained in equal volumes of
different gases if the pressure and temperature are the same.
COMBINED GAS LAW
P1V1 P2V2
29
n1T1 n2T2
IDEAL GAS LAW
PV nRT
PM RT
DALTON’S LAW OF PARTIAL PRESSURES

 The total pressure in a mixture of gases is the sum of the
individual partial pressures.
GRAHAM’S LAW OF DIFFUSION
 The rates of diffusion of two gases are inversely proportional to
the square roots of their densities.
r1 2 M2
r2 1 M1
30
Effusion of Gases
 Diffusion
 Gases move through space from a region of high
concentration to a region of low concentration
 You can smell an apple pie baking as the particles responsible
for the odor diffuse through the room
 Effusion
 Gas particles will escape through a small hole (orifice) in
a container
 Air will slowly leak out of a tire or balloon through pores in
the rubber
Graham’s Law of Effusion
1
rate of ef f usionof B MMA 2
rate of ef f usionof A MMB
 The rate at which gas B escapes divided by the rate at which

gas A escapes is equal to the square root of the ratio of the
molar mass of gas A to gas B
Effusion of Gases
Diffusion and Effusion of Gases
 Example Problem: A sample of hydrogen, H2, was found to
effuse through a pinhole 5.2 times as rapidly as the same
volume of unknown gas (at the same temperature and
pressure). What is the molecular weight of the unknown
gas?
You do it!
R H2 M u nk
R u nk M H2
M u nk
5.2
2.0 g/mol
M u nk
27
2.0 g/mol
M u nk 27(2.0 g/mol)= 54 g/mol 34
Partial Pressure
 Air is a mixture of gases.
 Gas laws do not depend on identity of gases.
 Pressure due to total moles gas present.
 The pressure exerted by a component of a gas mixture

is called the partial pressure for the component gas.
Partial Pressure
 Dalton’s law of partial pressures: The total pressure
(P) of a mixture of gases is the sum of the partial
pressures of the component gases (Pi).
P i
Pi
 Daltons Law can be expressed in terms of mole
fraction.
 Mole fraction (Xi) for a gas in a gas mixture is the moles
of the gas (ni) divided by the total moles gas present.
 The partial pressure of each gas is related to its mole
fraction. ni
Xi Pi Xi P
ntotal
Example Problem 5.4
 A scientist tries to generate a mixture of gases similar
to a volcano by introducing 15.0 g of water vapor, 3.5 g
of SO2, and 1.0 g of CO2 into a 40.0 L vessel held at
120.0˚C. Calculate the partial pressure of each gas and
the total pressure.
Example Problem 5.5
 A mixture has the mole fractions given in the following
table:
Gas N2 O2 H 2O SO2
Mole Fraction 0.751 0.149 0.080 0.020
 If the desired pressure is 750. torr, what should the

partial pressures be for each gas?
 If the gas is to be in a 15.0 L vessel held at 30°C, how

many moles of each substance are needed?
Stoichiometry of Reactions Involving Gases
 For reactions involving gases, the ideal gas law is used
to determine moles of gas involved in the reaction.
 Use mole ratios (stoichiometry)
 Connect number of moles of a gas to its temperature,

pressure, or volume with ideal gas law
PV nRT
Example Problem 5.6
 When an experiment required a source of carbon
dioxide, a student combined 1.4 g of sodium
bicarbonate (NaHCO3) with excess hydrochloric acid
(HCl). If the CO2 produced is collected at 722 torr and
17˚C, what volume will the gas occupy?
STP Conditions
 Standard temperature and pressure, STP, for a gas is
0˚C (273.15 K) and 1 atm.
 For one mole of gas at STP, the standard molar volume is

22.41 L (calculated using ideal gas law)
 This number provides a conversion factor for

stoichiometric problems that include gases, provided the
STP conditions are maintained.
Example Problem 5.7
 Carbon dioxide can be removed from a stream of gas
by reacting it with calcium oxide to form calcium
carbonate. If we react 5.50 L of CO2 at STP with excess
CaO, what mass of calcium carbonate will form?
KINETIC MOLECULAR THEORY OF GASES
 Gases are composed of molecules that are widely separated

from one another in otherwise empty space.
 The molecules move about at high speeds, traveling in straight
paths but in random directions.
 The molecules collide with one another but the collisions are
perfectly elastic.
 The average velocity of the molecules increases as the
temperature increases and decreases as the temperature
decreases.
 At a given temperature, the molecules of gases A and B have the
same average kinetic energy. An increase in mass is
compensated for by a decrease in average velocity.
43
Figure 5.1 – The Kinetic Molecular Model
Kinetic-Molecular Theory and Ideal versus Real Gases
 In many important practical settings, gases do not
always behave ideally, especially at very high pressure
and/or very low temperature.
 Nonideal gas behavior can be explained using Kinetic

Molecular Theory.
 Provides connections between observed macroscopic

properties of gases, the gas law equation, and the behavior of
gas molecules on a microscopic scale.
New Variables
 N, the number of gas particles
 m, the mass of the gas particle
 u, the average speed of a gas particle
Pressure and the Molecular Model
2
Nmu
P
3V
 Notes:
 N/V is the concentration of gas particles
 mu2 is a measure of the energy of the collisions
Average Kinetic Energy of Translational Motion
3RT
E
2N A
 Notes:
 R is the gas constant
 T is the Kelvin temperature
 NA is Avogadro’s number
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
Average Speed, u
1
3RT 2
u
MM
 The average speed is proportional to the square root of the

Kelvin temperature
 The average speed is proportional to the inverse of the
square root of the molar mass of the gas
Example
Real Gases and Limitations of the Kinetic Theory
 The volume of a gas particle is significant compared to
the “empty space” volume under high pressure
conditions.
 Mean free path decreases as pressure increases.
 Gas molecules are very close together.
 Therefore, volume of the gas particles becomes

significant.
 Kinetic molecular theory asserts that gas molecules move in straight lines and
interact only through perfectly elastic collisions.
 Gas molecules neither attract nor repel.
 Strength of attractive forces small compared to kinetic energy of gas

molecules.
 Attractive and repulsive forces are significant under conditions of low

temperature.
 Kinetic energy decreases with temperature.
 Gas molecules experience “sticky” collisions.
 Collision rate decreases, decreasing the pressure.

 The ideal gas model breaks down at high pressures and low temperatures.
 high pressure: volume of particles no longer negligible
 low temperature: particles move slowly enough to interact
Correcting the Ideal Gas Equation
 van der Waals equation is commonly used to describe the
behavior of real gases
an 2
P V nb nRT
V2
 a corrects for attractive forces.

 Molecules with stronger attractive forces have larger a values.
 b corrects for the volume occupied by gas molecules.

 Large molecules have larger b values.
Correcting the Ideal Gas Equation
 The van der Waals

constants a and b
are compound
specific.
 Both are zero in

gases behaving
ideally.
Example Problem 5.8
 An empty 49.0 L methane storage tank has an empty
mass of 55.85 kg and, when filled, has a mass of 62.07
kg. Calculate the pressure of CH4 in the tank at 21˚C
using both the ideal gas equation and the van der
Waals equation.
 What is the percentage correction achieved by using

the more realistic van der Waals equation?
End of Lecture Unit 1
58
• Introduction to Gases : Air
Pollution
• Properties of Gases
• Gas Laws
• Kinetic- Molecular Theory for
Gases
• Ideal and Real Gases
• Stoichiometry of Reactions
Engr. Edgie L. Estopace
B.S Chemical Engineering
B.S Chemistry
General Chemistry 2
LECTURE UNIT 2
 LIQUIDS, SOLIDS and PHASE CHANGES
1
Summary
1. Comparison between Liquids, Solids and Gases
2. Intermolecular Forces of Attraction in Liquids and
Solids
3. The Liquid State
3. Properties of Liquids
4. Phase Changes
 The Clausius-Clapeyron Equation
5. The Solid State
6. Types of Solids
7. Phase Diagrams
2
Recall Gases
• 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
Comparison between 3 states of Matter
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
 Schematic representation of the three

common states of matter.
gas
liquid solid
cool cool
heat heat
5
 Solids and liquids are condensed states.

 The atoms, ions, or molecules in solids and
liquids are much closer to one another than in
gases.
 Solids and liquids are highly incompressible.
 Liquids and gases are fluids.

 They easily flow.
 The intermolecular attractions in liquids
and solids are strong.
6
 If we compare the strengths of interactions

among particles and the degree of ordering
of particles, we see that
Gases< Liquids < Solids
7
Intermolecular Forces
 Intermolecular forces - the attractive and

repulsive forces between molecules.
 The attractive and repulsive intermolecular
forces are weak in comparison to bonding
forces.
 Intermolecular forces are largely
responsible for determining the structure
and properties of condensed phases.
 The principle of minimization of energy
applies here as well.
Dispersion Forces
 Dispersion forces are common to all

molecules.
 Also called London forces.
 Also referred to as instantaneous dipole-
induced dipole forces.
 Dipoles exist for two oppositely charged
points separated by some distance.
Dispersion Forces
London Forces are very weak.

 They are the weakest of the intermolecular
forces.
 This is the only attractive force in nonpolar
molecules.
 Consider Ar as an isolated atom.
10
Dispersion Forces
 In a group of Ar atoms the temporary

dipole in one atom induces other atomic
dipoles.
11
Dispersion Forces
 Similar effects occur in a group of I2

molecules.
The effect is shown in this movie.
12
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
Dispersion Forces
Dispersion Forces
 An instantaneous dipole occurs when a

fluctuation in electron density for an atom or
molecule produces a dipole.
 Instantaneous dipoles are short-lived and
constantly forming and disappearing.
 An induced dipole is created when an external
electric field forces a dipole to exist.
 A permanent dipole or an instantaneous dipole is
the source of the external electric field.
Dispersion Forces
 An external electric field distorts the electron

density around an atom or dipole, inducing a
dipole.
Dispersion Forces
 Individual dispersion forces are very weak.
 The sum of dispersion forces over an Avogadro’s
number of atoms results in a significant amount of
energy.
 Dispersion forces hold many liquids and solids
together.
 The strength of a dispersion force can be
estimated from the polarizability of a molecule.
 Polarizability is a measure of how susceptible a
molecule’s electron density is to perturbation by
external electric fields.
 Large molecules are more polarizable than smaller
molecules and experience stronger dispersion
forces.
Dipole-Dipole Forces
 Dipole-dipole forces are the attractive
and repulsive forces for molecules with a
permanent dipole.
 The charge at the poles of a dipole is
seldom more than a fraction of the charge
on an electron, making these forces weaker
than a chemical bond.
 Molecules with larger dipoles have stronger
dipole-dipole forces.
 Dipole-dipole forces are typically stronger
than dispersion forces.
Dipole-dipole interactions
 Consider BrF a polar molecule.
21
 Dipole-dipole
forces for 50
polar molecules.
 At any given
time, the
number of
attractive
interactions is
greater than the
number of
repulsive
interactions.
Example 2.1
Example 2.1, (Cont’d)
Hydrogen Bonding
 Hydrogen bonds are a special case of
dipole-dipole forces.
 Hydrogen bonds are especially strong
compared to dipole-dipole forces.
 Hydrogen bonds occur only in compounds
containing hydrogen covalently bonded to
the highly electronegative elements F, O, or
N.
 The strong dipole created in these types of
covalent bonds creates a strong dipole-dipole
interaction with similar bonds.
Hydrogen Bonding
• Unusually strong type of dipole force
• H attached to a N, O, or F
• The H from one molecule can bond to the
negative end of the dipole of another
• Dipole arises from the difference in the
electronegativity between H and (N, O, or F)
• Small size of H allows the unshared pair from
the negative end of the dipole to approach the H
closely
• HF, H2O and NH3: unusually high boiling
points as a result of hydrogen bonding
Hydrogen Bonding
Hydrogen bonding
 Consider H2O a very polar molecule.
27
Water
• Hydrogen bonding in water accounts for

• High specific heat
• High boiling point
• Higher density of the liquid phase relative to
the solid
Figure 2.2
Hydrogen Bonding
Hydrogen Bonding
31
Example 2.2
Intermolecular Forces Vs. Covalent bond
 Intermolecular forces are weak

compared to the average covalent bond.
 The large number of intermolecular

forces make intermolecular forces a key
factor in determining the bulk properties
of materials.
Intermolecular Forces
 Carbon atoms within a graphite sheet held together

by covalent bonds.
 Intermolecular forces hold graphite sheets together.
Example Problem 2.3
 Which type(s) of intermolecular forces

need to be overcome to convert each of
the following liquids to gases?
 CH4
 CH3F
 CH3OH
Example 2.4
The Liquid State
Viscosity
 Viscosity is the resistance to flow.
 For example, compare how water pours out
of a glass compared to molasses, syrup or
honey.
 Oil for your car is bought based on this
property.
38
The Liquid State
Viscosity = Resistance to flow.

• High viscosity = slow flow.
• Viscosity decreases with increasing temperature
• Strong IMF results to higher viscosity
 low viscosity: water, ethanol, gasoline…

 high viscosity: honey, corn syrup …
The Liquid State
Surface Tension
 Surface tension is a measure of the unequal
attractions that occur at the surface of a liquid.
 The molecules at the surface are attracted
unevenly.
 Strong IMF results to high surface tension
 explains why rain droplets are spherical
40
Surface Tension
 Surface tension is
the result of
molecules at the
surface of a liquid
experiencing
fewer
intermolecular
forces than liquid
molecules inside
the bulk liquid.
Figure 2.2 – Surface Tension of Water
The Liquid State
 Floating paper clip demonstration of

surface tension.
43
The Liquid State
Capillary Action
 Capillary action is the ability of a liquid to
rise (or fall) in a glass tube or other
container
44
The Liquid State
 Cohesive forces are the forces that hold

liquids together.
 Adhesive forces are the forces between
a liquid and another surface.
 Capillary rise implies that the:
 Adhesive forces > cohesive forces
 Capillary fall implies that the:
 Cohesive forces > adhesive forces
45
The Liquid State
 Water exhibits a capillary rise.
 Mercury exhibits a capillary
fall.
Water Mercury
46
The Liquid State
 Capillary action also affects the meniscus of liquids.
47
Phase Changes
Evaporation
 Evaporation is the process in which
molecules escape from the surface of a
liquid and become a gas.
 Evaporation is temperature dependent.
48
Phase Changes
endothermic
process
(heat added)
exothermic
process
(heat released)
Phase Changes
• In an open container, evaporation continues
until all the liquid is converted into vapor
• In a closed container, the process of
vaporization is countered by the process of
condensation:
• Liquid ⇌ Vapor
• The double arrow indicates a dynamic
equilibrium
Equilibrium
• When the rate at which the liquid vaporizes is
equal to the rate at which the vapor
condenses, a dynamic equilibrium is
established
• The liquid level in the container does not
change
• Molecules are entering the vapor phase from
the liquid and condensing from the vapor
phase to the liquid at the same rate
Equilibrium in Bromine
Phase Changes
Vapor Pressure
 Vapor pressure is the pressure exerted by a
liquid’s vapor on its surface at equilibrium.
 Vapor Pressure (torr) and boiling point for
three liquids at different temperatures.
0oC 20oC 30oC normal boiling point
diethyl ether 185 442 647 36oC
ethanol 12 44 74 78oC
water 5 18 32 100oC
 What are the intermolecular forces in each of these
compounds?
53
You do it!
Vapor Pressure
Phase Changes
Vapor Pressure as a function of temperature.
55
Phase Changes
Boiling Points and Distillation

 The boiling point is the temperature at
which the liquid’s vapor pressure is equal
to the applied pressure.
 The normal boiling point is the boiling
point when the pressure is exactly 1 atm.
 Distillation is a method we use to
separate mixtures of liquids based on
their differences in boiling points.
56
Boiling Point
• When heat is applied to a liquid in an open
container, bubbles eventually form at the
bottom
• At a certain temperature, large bubbles form
throughout the liquid; i.e., the liquid boils
• The temperature at which a liquid boils depends on
the pressure above it
• If the pressure is 1 atm, the temperature at which the
liquid boils is called the normal boiling point
• When the term boiling point is used, the normal boiling
point is implied
• The boiling point is the temperature at which
the vapor pressure equals the prevailing
pressure
Boiling Point
• Variation on atmospheric pressure will

change the boiling point
• At high elevation, atmospheric pressure is
lower, so the boiling point is lower
• To elevate the boiling point and allow food
to cook more quickly, a pressure cooker can
be used
Figure 2.3 - Boiling
Phase Changes
 Clausius-Clapeyron equation
 determine vapor pressure of a liquid at a
new T
 determine what T we must heat something
to get a specified vapor pressure
 way to determine Hvap if we know pressure
at 2 T’s
P2 ΔHvap 1 1
ln =– –
P1 R T2 T1
60
The Clausius-Clapeyron Equation
• For many purposes, a two-point equation is useful
• Two pressures
• Two temperatures
P2 Hvap 1 1
ln
P1 R T1 T2
• Notes:
• Temperatures must be in Kelvin
• R = 8.314 J/mol·K
• ΔHvap must be in J for use with this value for R
Sublimation
• Sublimation is the process by which a solid

passes directly into the vapor phase without
first being converted to a liquid
• Sublimation can happen only at a temperature
below the triple point
• Water can sublime if the pressure is reduced
• Freeze drying
• Cold winter days
• Iodine sublimes readily because its triple point
pressure is much higher than that of water
Figure 2.4
The Liquid State
 Example 2.6: Arrange the following

substances in order of increasing boiling
points.
C2H6, NH3, Ar, NaCl, AsH3
You do it!
Ar < C2H6 < AsH3 < NH3 < NaCl
nonpolar nonpolar polar very polar ionic
London London dipole-dipole H-bonding ion-ion
64
The Solid State
Normal Melting Point

 The normal melting point is the
temperature at which the solid melts
(liquid and solid in equilibrium) at exactly
1.00 atm of pressure.
 The melting point increases as the
strength of the intermolecular attractions
increase.
65
Sublimation and the Vapor Pressure of Solids
Sublimation
 In the sublimation process the solid
transforms directly to the vapor phase
without passing through the liquid phase.
 Solid CO2 or “dry” ice does this well.
sublimation
solid condensation
gas
66
Types of Solid
 Amorphous solids do not have a well ordered

molecular structure.
 Examples of amorphous solids include waxes,
glasses, asphalt.
 Crystalline solids have well defined structures
that consist of extended array of repeating
units called unit cells.
 Crystalline solids display X-ray diffraction patterns
which reflect the molecular structure.
67
Structure of Crystals
 Unit cells are the smallest repeating unit of a
crystal.
 As an analogy, bricks are repeating units for
buildings.
 There are seven basic crystal systems.
68
 We shall look at the three variations of the
cubic crystal system.
 Simple cubic unit cells.
 The balls represent the positions of atoms,
ions, or molecules in a simple cubic unit cell.
69
 In a simple cubic unit cell each atom, ion,
or molecule at a corner is shared by 8
unit cells
 Thus 1 unit cell contains 8(1/8) = 1 atom,
ion, or molecule.
70
 Body centered cubic (bcc) has an additional atom, ion, or
molecule in the center of the unit cell.
 On a body centered cubic unit cell there are 8 corners + 1
particle in center of cell.
 1 bcc unit cell
 contains 8(1/8) + 1 = 2 particles.
71
 A face centered cubic (fcc) unit cell has a

cubic unit cell structure with an extra
atom, ion, or molecule in each face.
72
 A face centered cubic unit cell has 8
corners and 6 faces.
 1 fcc unit cell contains
 8(1/8) + 6(1/2) = 4 particles.
73
 A unit cell is the smallest collection of atoms that
displays all the features of the crystal structure.
 Three types of cubic unit cells - simple cubic (sc)
containing 1/8 each of 8 corner atoms, body-centered
cubic (bcc) containing one additional atom within, and
face-centered cubic (fcc) with an additional 1/2 each of 6
atoms along the faces.
 To determine the number of complete

atoms per unit cell:
1 1
fcc = (# face-center atoms) (# corner atoms) 4
2 8
1
bcc = (# body-center atoms) (# corner atoms) 2
8
1
sc (# corner atoms) 1
8
Condensed Phases - Solids
 Coordination number is the number of

atoms immediately adjacent to any given
atom.
 Simple cubic has a coordination number of
6.
 Body-centered cubic has a coordination
number of 8.
 FCC structures have a coordination number
of 12.
Bonding in Solids
 Molecular Solids have molecules in each
of the positions of the unit cell.
 Molecular solids have low melting points,
are volatile, and are electrical insulators.
 Examples of molecular solids inlude:
 sugars
77
Bonding in Solids
 Covalent Solids have atoms that are
covalently bonded to one another
 Some examples of covalent solids are:
 Diamond, graphite, SiO2 (sand), SiC
78
Bonding in Solids
 Ionic Solids have ions that occupy the
positions in the unit cell.
 Examples of ionic solids include:
 CsCl, NaCl, ZnS
79
Bonding in Solids
 Metallic Solids may be thought of as

positively charged nuclei surrounded by
a sea of electrons.
 The positive ions occupy the crystal
lattice positions.
 Examples of metallic solids include:
 Na, Li, Au, Ag, ……..
80
Solids: Network Covalent, Ionic and Metallic
• Network covalent solids

• Continuous network of covalent bonds
• Crystal is one large molecule
• Ionic solids
• Oppositely-charged ions held together by
strong electrical forces
• Metallic solids
• Structural unit are +1, +2 and +3 metals with
associated electrons
Figure 2.11
Bonding in Solids
 Variations in Melting Points for Molecular Solids
 What are the intermolecular forces in each solid?
 Compound Melting Point (oC)

 ice 0.0
 ammonia -77.7
 benzene, C6H6 5.5
 napthalene, C10H8 80.6
 benzoic acid, C6H5CO2H 122.4
83
Bonding in Solids
 Variations in Melting Points for Covalent Solids

 Substance Melting Point (oC)
 sand, SiO2 1713
 carborundum, SiC ~2700
 diamond >3550
 graphite 3652-3697
84
Bonding in Solids
• Variations in Melting Points for Ionic Solids
• Compound Melting Point (oC)
 LiF 842
 LiCl 614
 LiBr 547
 LiI 450
 CaF2 1360
 CaCl2 772
 CaBr2 730
 CaI2 740
85
Bonding in Solids
 Variations in Melting Points for Metallic Solids
 Metal Melting Point (oC)
 Na 98
 Pb 328
 Al 660
 Cu 1083
 Fe 1535
 W 3410
86
Phase Diagrams
• Phase diagrams are graphical representations
of the pressure and temperature dependence
of a pure substance
• Pressure on the y-axis
• Temperature on the x-axis
• Three places to consider
• In a region, one phase exists
• On a line, two phases exist in equilibrium
• At a point, three phases exist in equilibrium
Figure 2.5 – A Phase Diagram
Phase Diagram of Water
• Curve AB is the vapor pressure-temperature
curve
• Curve AC is the vapor pressure curve of ice
• Line A-D gives the temperature-pressure
dependence for ice in equilibrium with water
• Point A is the triple point
• All three phases are in equilibrium
• There is only one triple point for a pure substance
• For water, the triple point is at 0.01 C
Example 9.3
Figure 9.7
Phase Diagrams
Solid Liquid
Melting point Supercritical
curve fluid
critical point
Pressure (atm)
melting
freezing vaporization
condensation
Vapor-pressure
triple point curve
sublimation
Gas
deposition
Temperature (°C)
Phase Diagrams
Triple point
Three phases in equilibrium. T and P are
fixed. Water T = 0.01°C, P = 4.58 mmHg
CO2 T = -57°C, P = 5.2 atm
Critical point
The end of the liquid/gas equilibrium line. It occurs at
the critical temperature, Tc and critical pressure, Pc
Water Tc = 374°C, Pc = 218 atm
CO2 Tc = 31°C, Pc = 73 atm
Above Tc a gas cannot be liquefied (at any P)
Critical Temperature and
Pressure
Above Tc and Pc the substance is neither a
liquid nor a gas. It is a supercritical fluid.
It has:
• a density characteristic of a liquid.
• flow properties of a gas.
Supercritical CO2 is an important solvent. It is used:

• to extract caffeine from coffee beans
• as a dry-cleaning fluid
Water Phase Diagram
normal fp normal bp
760
Pressure (mm Hg)
Solid Liquid Gas
4.58 triple point
0 0.01 100
Temperature (°C)
For most materials, the solid/liquid line has a positive slope.

Water is unusual. Ice can be melted by increased P !
Water: A Liquid with Unusual Properties
Table 11.4 Unusual Properties of Water
Physical Comparison with Importance in
Property Other Substances and Biological Environment
Specific heat capacity Highest of all liquids and Moderates T in the environment and in
(4.18 J g-1 °C-1) solids except NH3 organisms; climate affected by
movement of water (e.g., Gulf Stream)
Heat of fusion Highest of all molecular Freezing water releases large quantity
(333 J/g) solids except NH3 of thermal E; used to save crops from
freezing by spraying them with liq. water
Heat of vaporization Highest of all molecular Condensation of water vapor in clouds
(2250 J/g) substances releases large quantities of thermal E
fueling storms
Surface tension Highest of all molecular Contributes to capillary action in plants
(7.3 x 10-2 J/m2) liquids causes formation of spherical droplets;
supports insects on water surfaces
Thermal conductivity Highest of all molecular Aids heat transfer in organisms;
(0.6 J s-1 m-1 °C-1) liquids rapidly cools organisms immersed in
cold water, causing hypothermia
 Our understanding of
the intermolecular
forces of attraction
existing in solids and
liquids will be use for
describing solutions
 Solutions will be the
topics of the next
unit!
97
Summary
1. Comparison between Liquids, Solids and Gases
2. Intermolecular Forces of Attraction in Liquids and
Solids
3. The Liquid State
3. Properties of Liquids
4. Phase Changes
 The Clausius-Clapeyron Equation
5. The Solid State
6. Types of Solids
7. Phase Diagrams
98
General Chemistry 2
LECTURE UNIT 2
 LIQUIDS, SOLIDS and PHASE CHANGES
99
CHM12-3
Lecture Unit No.3
 SOLUTIONS
– Physical Properties
 Engr. E. L. Estopace
 School of Chemical Engineering and Chemistry
 Mapua Institute of Technology 1
Scope
1. Types of Intermolecular Forces of
Attraction
2. Types of Concentration Units
3. Factors Affecting Solubility
4. Colligative Properties of Solutions
5. Determining Molar Mass Using
Colligative Properties of Solutions
6. Colligative Properties of
Electrolytes
2
INTRODUCTION:
Solutions in Everyday Life
• Morning coffee
• Solutions of solids (sugar, coffee) in liquid (water)
• Gasoline
• Solution of liquid hydrocarbons
• Soda
• Solution of sugar, water and carbon dioxide
• Air
• Solution of oxygen and nitrogen
INTERMOLECULAR FORCES of ATTRACTION
 STRENGTH OF IMF
 London<dipole-dipole<H-bonding<ion-dipole<ionic bonding
SUMMARY
IONIC  ionic bonding
NONPOLAR COMPOUNDS  London Dispersion forces
POLAR MOLECULES
 With ions  Ion-dipole
 With H bonded to O, F and N  H-bonding
 Without hydrogen  dipole-dipole
4
Solutions
 Solutions are homogeneous mixtures of two
or more substances.
– Dissolving medium is called the solvent.
– Dissolved species are called the solute.
 There are three states of matter (solid, liquid,
and gas) which when mixed two at a time
gives nine different kinds of mixtures.
–.
5
Solutions
 Existin all 3 physical states
 Can be mixtures of solids, liquids and
gases
Type of Solution Examples

Gas in gas Air
Gas in liquid Carbonated drinks.
Gas in solid Hydrogen in Pd metal.
Liquid in liquid Motor oil, vinegar.
Solid in liquid Ocean water, sugar-water.
Solid in solid Bronze, 14K gold.
Solutions
Like dissolves like
If solute and solvent intermolecular forces are:
• Similar… the pair will be soluble.
 polar dissolves polar;
 non-polar dissolves non-polar
• Dissimilar
= insoluble.
Solutions
Substances dissolve when:
solvent-solute attraction > solvent-solvent
attraction,
and > solute-solute
attraction
Solutions
Miscible liquids dissolve in all proportions.
e.g. ethanol and water (both H-bonded polar liquids).
Immiscible liquids form distinct separate phases.

e.g. gasoline (non-polar) and water (polar).
Carefully layered liquids

(different d):
(a) colorless CCl4; green

NiCl2(aq); colorless C7H16(l).
(b) After mixing and settling.

Solutions
Name Formula Solubility (g/100g H2O @20°C)
methanol CH3OH miscible
ethanol C2H5OH miscible
London
1-propanol C3H7OH miscible
forces
1-butanol C4H9OH 7.9
increasing
1-pentanol C5H11OH 2.7
1-hexanol C6H13OH 0.6
Solubility in water decreases as alcohols grow larger

because:
Solute-solute attraction grows
Solute-solvent attraction stays ≈ constant.
Solutions
 Nonpolar molecules essentially “slide”

in between each other.
– For example, carbon tetrachloride and
benzene are very miscible.
H
Cl H C H
C C
Cl C Cl
C C
Cl H C H
H 11
WAYS OF EXPRESSING
CONCENTRATION OF
SOLUTIONS
12
Percent by mass
1. % by mass/weight of solute
mass of solute
% w/w = 100%
mass of solution
13
Percent by mass
Mass Solute
Mass fraction =
Total Mass of Solution
Weight percent = Mass fraction x 100%
Example
Saline solutions (NaCl in water) are often used in
medicine. What is the weight percent of NaCl in a solution
of 4.6 g of NaCl in 500. g of water?
4.6 g
mass fraction = = 0.0091
500. g + 4.6 g
weight percent = 0.0091 x 100% = 0.91 %
Molarity
2. Molarity
moles of solute
M =
Liters of solution
• V of solution not solvent.
• Shorthand: [NaOH] =1.00 M
The brackets [ ] represent

“molarity of ”
15
Molarity
Calculate the molarity of sodium sulfate in a
solution that contains 36.0 g of Na2SO4 in
750.0 mL of solution.
36.0 g = 0.2534 mol
nNa2SO4 =
142.0 g/mol
0.2534 mol
[Na2SO4 ] = Unit change!
0.7500 L (mL to L)
[Na2SO4 ] = 0.338 mol/L = 0.338 M

Molality and Mole Fraction
 Molality is a concentration unit based on
the number of moles of solute per
kilogram of solvent.
moles of solute
m
kg of solvent
in dilute aqueous solutions molarity and
molality are nearly equal
17
 Mole fraction is the number of moles of one
component divided by the moles of all the
components of the solution
– Mole fraction is literally a fraction using moles of one
component as the numerator and moles of all the
components as the denominator.
 In a two component solution, the mole fraction of
one component, A, has the symbol XA.
number of moles of A
XA
number of moles of A + number of moles of B
18
 The mole fraction of component B - XB
number of moles of B
XB
number of moles of A + number of moles of B
Note that X A X B 1
The sum of all the mole fractions must equal 1.00.
19
Calculate the molality of a solution that contains
7.25 g of benzoic acid C6H5COOH, in 2.00 x 102
mL of benzene, C6H6. The density of benzene is
0.879 g/mL. 1 mol C6H5COOH = 122 g
You do it!
? mol C 6 H 5COOH 7.25g C 6 H 5COOH 1 mL C 6 H 6

kg C 6 H 6 200.0 mL C 6 H 6 0.879 g C 6 H 6
1000 g C 6 H 6 1 mol C 6 H 5COOH
0.338 m C 6 H 5COOH
1 kg C 6 H 6 122 g C 6 H 5COOH
20
 Example : What are the mole fractions of
glucose and water in a 10.0% glucose
solution (Example 14-1)?
You do it!
2
In 1.00 10 g of this solution t here are
10.0 g of glucose and 90.0 g of water.
? mol C 6 H12O 6 10.0 g C 6 H12O 6
1 mol C 6 H12O 6
0.0556 mol C 6 H12O 6
180 g C 6 H12O 6
21
 Example 14-3: What are the mole fractions of
glucose and water in a 10.0% glucose solution ?
1 mol H 2 O
? mol H 2O 90.0 g H 2O 5.00 mol H 2 O
18 g H 2 O
22
 Now we can calculate the mole fractions.
5.00 mol H 2 O
X H 2O
5.00 mol H 2 O + 0.0556 mol C 6 H 12 O 6
0.989
0.0556 mol C 6 H 12 O 6
X C6 H12 O 6
5.00 mol H 2 O + 0.0556 mol C 6 H 12 O 6
0.011
1.00 0.989 0.011
23
Parts per Million, Billion and Trillion
% = Parts per hundred = mass solute x 102
mass solution
Very dilute = low mass fraction.

Units for high dilution (trace solute):
Parts per million (ppm) = mass solute x 106

mass solution
Parts per billion (ppb) = mass solute x109

mass solution
Parts per trillion (ppt) = mass solute x1012

mass solution
Parts per Million, Billion and Trillion
1 ppm of solute in water = 1 mg / 1000 g of

solution
Since 1L of water has a mass ≈ 1000 g.

1 ppm ≈ 1 mg/L
Similarly 1 ppb ≈ 1 μg/L

1 ppt ≈ 1 ng/L
Conversions Between Concentration Units
• To convert between units, first decide on a fixed amount
of solution to start with:
When the original Choose

concentration is
Mass percent 100 g solution
Molarity (M) 1.00 L solution
Molality (m) 1.00 kg solvent
Mole fraction (X) 1.00 mol solution

Changing Molarity to Molality
If we know the
density of the
solution, we can
calculate the
molality from the
molarity, and vice
versa.
Solubility
• The process by which one substance
dissolves in another is ordinarily a physical
change
• The resulting mixture is a solution
• Solutions may be classified by the relative
amount of solute and solvent
• Saturated: maximum amount of solute
• Unsaturated: less than maximum amount of
solute
• Supersaturated: more than maximum amount of
solute
Figure 3.1 – Sugar Crystals
Factors Affecting
Solubility
Figure 3.2 – Solubility and Temperature
Supersaturation
“seed” crystal
of sodium The solution warms…
acetate
…heat is released as crystals form
Excess sodium
Supersaturated acetate begins to More and more
sodium acetate crystallize around crystallizes until
solution the seed a saturated
solution remains.
Dissolution of Gases in Liquids
 Polar gases are more soluble in water
than nonpolar gases.
– This is the “like dissolves like” rule in action.
 Polar gases can hydrogen bond with water
 Some polar gases enhance their solubility
by reacting with water. + -
HBr + H 2 O H 3O aq Br aq
strong acid
SO 2 + H 2 O H 2SO 3 aq
H 2O -
+
H 2SO 3(aq) H 3O aq HSO 3 aq
33
weak acid
Effect of Temperature on Solubility
 According to LeChatelier’s Principle when stress is
applied to a system at equilibrium, the system
responds in a way that best relieves the stress.
– Since saturated solutions are at equilibrium, LeChatelier’s
principle applies to them.
 Possible stresses to chemical systems include:
1. Heating or cooling the system.
2. Changing the pressure of the system.
3. Changing the concentrations of reactants or products.
34
 What will be the effect of heating or cooling the
water in which we wish to dissolve a solid?
– It depends on whether the dissolution is exo- or
endothermic.
 For an exothermic dissolution, heat can be
considered as a product.
H 2O + -
LiBr s Li aq Br aq 48.8kJ / mol
 Warming the water will decrease solubility and cooling the
water will increase the solubility.
 Predict the effect on an endothermic dissolution like this one.
H 2O + -
KMnO 4 s 43.6 kJ / mol K aq MnO 4 aq
35
36
• For a gas, the dissolution process is

exothermic, so the reverse process
(gas evolving from solution) is
endothermic
• Therefore, for gases, solubility
decreases with increasing
temperature
Effect of Pressure on Solubility
 Pressure changes have little or no effect
on solubility of liquids and solids in
liquids.
– Liquids and solids are not compressible.
 Pressure changes have large effects on
the solubility of gases in liquids.
– Sudden pressure change is why
carbonated drinks fizz when opened.
– It is also the cause of several scuba diving
related problems including the “bends”.
38
• 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):
• Cg = kPg, where
• Pg is the partial pressure of the gas over the
solution
• Cg is the concentration of the gas
• k is a constant (the Henry’s Law constant)
 The effect of pressure on the solubility of gases in
liquids is described by Henry’s Law.
Pgas
gas
kkMM
gasgas
where M
where M gas
gas
molar
molarconcentrat ion of
concentrat iongasof gas
k = Henry' s Law constant, unique number for each
gas - liquid combinatio n
Pgas = partial pressure of gas
40
Colligative Properties of
Solutions
 Colligative properties are properties of
solutions that depend solely on the
number of particles dissolved in the
solution.
– Colligative properties do not depend on the
kinds of particles dissolved.
 Colligative properties are a physical
property of solutions.
41
Colligative Properties of
Solutions
 There are four common types of
colligative properties:
1. Vapor pressure lowering
2. Freezing point depression
3. Boiling point elevation
4. Osmotic pressure
 Vapor pressure lowering is the key to
all four of the colligative properties.
42
Lowering of Vapor Pressure and
Raoult’s Law
 Addition of a nonvolatile solute to a
solution lowers the vapor pressure of the
solution.
– The effect is simply due to fewer solvent
molecules at the solution’s surface.
– The solute molecules occupy some of the
spaces that would normally be occupied by
solvent.
 Raoult’s Law models this effect in ideal
solutions. 43
Raoult’s Law
 Derivation of Raoult’s Law.
0
Psolvent X solvent Psolvent
where Psolvent vapor pressure of solvent in solution
0
Psolvent vapor pressure of pure solvent
X solvent mole fraction of solvent in solution
44
Raoult’s Law
 Lowering of vapor pressure, Psolvent, is defined
as:
0
Psolvent Psolvent Psolvent
0 0
Psolvent - ( X solvent)( P solvent )
0
(1 X solvent)P solvent
45
Raoult’s Law
 Remember that the sum of the mole
fractions must equal 1.
 Thus Xsolvent + Xsolute = 1, which we can
substitute into our expression.
X solute 1 - X solvent
0
Psolvent X solute P
solvent
which is Raoult' s Law

46
Raoult’s Law
 This graph shows how the solution’s vapor
pressure is changed by the mole fraction of the
solute, which is Raoult’s law.
47
Boiling Point Elevation
solution raises the boiling point of the
solution above that of the pure solvent.
– This effect is because the solution’s vapor
pressure is lowered as described by Raoult’s
law.
– The solution’s temperature must be raised to
make the solution’s vapor pressure equal to
the atmospheric pressure.
 The amount that the temperature is
elevated is determined by the number of
moles of solute dissolved in the solution.
48
 Boiling point elevation relationship is:

Tb Kbm
where : Tb boiling point elevation
m molal concentrat ion of solution
K b molal boiling point elevation constant
for the solvent
49
 Example 14-4: What is the normal boiling
point of a 2.50 m glucose, C6H12O6,
solution?
Tb K bm
Tb (0.512 0 C/m)( 2.50m)
Tb 1.280 C
Boiling Point of the solution = 100.00 C + 1.280 C = 101.280 C
50
Freezing Point Depression
solution lowers the freezing point of the
solution relative to the pure solvent.
 See table 14-2 for a compilation of boiling
point and freezing point elevation
constants.
51
 Relationship for freezing point depression
is: T K m
f f
where: Tf freezing point depression of solvent
m molal concentration of soltuion
Kf freezing point depression constant for solvent
52
 Notice the similarity of the two
relationships for freezing point depression
and boiling point elevation.
Tf K f m vs. Tb Kbm
 Fundamentally, freezing point depression and boiling
point elevation are the same phenomenon.
– The only differences are the size of the effect which is
reflected in the sizes of the constants, Kf & Kb.
 This is easily seen on a phase diagram for a solution.
53
 Example 14-5: Calculate the freezing

point of a 2.50 m aqueous glucose
solution. Tf K f m
Tf (1.86 0 C/m)( 2.50m)
Tf 4.650 C
Freezing Point of solution = 0.000 C - 4.650 C = - 4.650 C
54
 Example 14-6: Calculate the freezing

point of a solution that contains 8.50 g
of benzoic acid (C6H5COOH, MW =
122) in 75.0 g of benzene, C6H6.
You do it!
55
1. Calculate molality!
? mol C 6 H 5 COOH 8.50 g C 6 H 5 COOH
kg C 6 H 6 0.0750 kg C 6 H 6
1 mol C 6 H 5 COOH
0.929m
122 g C 6 H 5 COOH
2. Calculate the depression for this solution.
Tf Kf m
Tf (5.12 0 C/m)( 0.929m) 4.76 0 C
F.P. = 5.480 C - 4.76 0 C = 0.72 0 C
56
Determination of Molecular
Weight by Freezing Point
Depression
 The size of the freezing point depression
depends on two things:
1. The size of the Kf for a given solvent, which are
well known.
2. And the molal concentration of the solution which
depends on the number of moles of solute and
the kg of solvent.
 If Kf and kg of solvent are known, as is
often the case in an experiment, then we
can determine # of moles of solute and use
it to determine the molecular weight. 57
Depression
 Example 14-7: A 37.0 g sample of a new
covalent compound, a nonelectrolyte, was
dissolved in 2.00 x 102 g of water. The
resulting solution froze at -5.58oC. What is
the molecular weight of the compound?
58
Depression
T K m thus the
f f
Tf 5.580 C
m 3.00m
Kf 1.860 C
In this problem there are
200 mL 0.200 kg of water.
? mol compound in 0.200 kg H 2 O = 3.00 m 0.200 kg
0.600 mol compound
37 g
Thus the molar mass is 61.7 g/mol
0.600 mol
59
Colligative Properties and
Dissociation of Electrolytes
 Electrolytes have larger effects on boiling point
elevation and freezing point depression than
nonelectrolytes.
– This is because the number of particles released in
solution is greater for electrolytes
 One mole of sugar dissolves in water to produce
one mole of aqueous sugar molecules.
 One mole of NaCl dissolves in water to produce
two moles of aqueous ions:
– 1 mole of Na+ and 1 mole of Cl- ions
60
 Remember colligative properties depend on
the number of dissolved particles.
– Since NaCl has twice the number of particles we
can expect twice the effect for NaCl than for
sugar.
 The table of observed freezing point
depressions in the lecture outline shows this
effect.
61
 Ion pairing or association of ions
prevents the effect from being exactly
equal to the number of dissociated ions
62
 The van’t Hoff factor, symbol i, is used to
introduce this effect into the calculations.
 i is a measure of the extent of ionization or
dissociation of the electrolyte in the
solution.
Tf actual
i
Tf if nonelectrolyte
63
 i has an ideal value of 2 for 1:1 electrolytes like NaCl,
KI, LiBr, etc.
Na + Cl- H 2O
Na +aq Cl-aq 2 ions
formula unit
 i has an ideal value of 3 for 2:1 electrolytes like
K2SO4, CaCl2, SrI2, etc.
Ca 2+ Cl-2 H 2O
Ca 2aq+ 2 Cl-aq 3 ions
formula unit
64
 Example 14-8: The freezing point of 0.0100 m
NaCl solution is -0.0360oC. Calculate the van’t
Hoff factor and apparent percent dissociation of
NaCl in this aqueous solution.
 meffective = total number of moles of solute
particles/kg solvent
 First let’s
T calculate the i factor.
f actual K f meffective meffective
i
Tf if nonelectrolyte K f mstated mstated
65
Tf actual K f meffective meffective

i
Tf if nonelectrolyte K f mstated mstated
Tf actual 0.0360 0 C
Tf actual K f meffective meffective
Kf 1.86 0 C m
meffective 0.0194 m
meffective 0.0194 m i 194
.
mstated 0.0100 m
66
Osmotic Pressure
 Osmosis is the net flow of a solvent between
two solutions separated by a semipermeable
membrane.
– The solvent passes from the lower concentration
solution into the higher concentration solution.
 Examples of semipermeable membranes
include:
1. cellophane and saran wrap
2. skin
3. cell membranes
67
Osmotic Pressure
semipermeable membrane
H2O H2O
sugar dissolved H2O H2O net2solvent flow

H2O O
in water
H2O H2O
68
Osmotic Pressure
69
Osmotic Pressure
 Osmosis is a rate controlled phenomenon.
– The solvent is passing from the dilute solution into the
concentrated solution at a faster rate than in opposite
direction, i.e. establishing an equilibrium.
 The osmotic pressure is the pressure exerted by
a column of the solvent in an osmosis
experiment.
MRT
where: = osmotic pressure in atm
M = molar concentration of solution
L atm
R = 0.0821
mol K
70
T = absolute temperature
Osmotic Pressure
 For very dilute aqueous solutions,

molarity and molality are nearly equal.
M m
mRT
for dilute aqueous solutions only
71
Osmotic Pressure
 Osmotic pressures can be very large.
– For example, a 1 M sugar solution has an
osmotic pressure of 22.4 atm or 330 p.s.i.
 Since this is a large effect, the osmotic
pressure measurements can be used to
determine the molar masses of very large
molecules such as:
1. Polymers
2. Biomolecules like
• proteins
• ribonucleotides 72
Osmotic Pressure
 Example 14-18: A 1.00 g sample of a
biological material was dissolved in enough
water to give 1.00 x 102 mL of solution. The
osmotic pressure of the solution was 2.80
torr at 25oC. Calculate the molarity and
approximate molecular weight of the
material.
You do it!
73
Osmotic Pressure
MRT M
RT
1 atm
? atm = 2.80 torr 0.00368 atm =
760 torr
0.00368 atm 4
M = L atm
150
. 10 M
0.0821 mol K 298 K
74
Osmotic Pressure
MRT M
RT
1 atm
? atm = 2.80 torr 0.00368 atm =
760 torr
0.00368 atm 4
M = L atm
150
. 10 M
0.0821 mol K
298 K
?g 1.00 g 1L
4
6.67 10 4 g mol
mol 0.100 L 150. 10 M
typical of small proteins
75
End of Lecture 3
 Human Beings are solution chemistry in
action!
76
Scope
1. Types of Intermolecular Forces of
Attraction
2. Types of Concentration Units
3. Factors Affecting Solubility
4. Colligative Properties of Solutions
5. Determining Molar Mass Using
Colligative Properties of Solutions
6. Colligative Properties of
Electrolytes
77
CHM12-3
Lecture Unit No.3
 SOLUTIONS
– Physical Properties
 Engr. E. L. Estopace
 School of Chemical Engineering and Chemistry
 Mapua Institute of Technology 78
CHM12-3
Lecture Unit 4
Reactions in Aqueous Solutions
1
Scope
1. Types of Reactions in Aqueous Solutions
 Precipitation reactions, Acid-Base, Redox
 Net Ionic Equation
 Dilution of Solution
2. Theories of Acids and Bases
3. Strengths of Acids
4. Acid- Base Reaction/ Titration
5. Redox reactions
2
A Review on Classification of Solute
 Electrolytes are soluble compounds that

conduct current when dissolved in water.
 Weak electrolytes dissociate partially into ions in
solution.
 Strong electrolytes dissociate completely into
ions in solution.
 Nonelectrolytes do not dissociate into ions
in solution.
a) Sugar, a nonelectrolyte, does not conduct current when dissolved in water.

b) Acetic acid, a weak electrolyte, weakly conducts current when dissolved in
water.
c) Potassium chromate, a strong electrolyte, strongly conducts current when
dissolved in water.
 When a covalently bonded material

dissolves in water and the molecules
remain intact, they do not conduct current.
These compounds are nonelectrolytes.
C6 H12O6 (s) 
 C6 H12O6 (aq)
 The water molecules are not shown explicitly,
although their presence is indicated by the “(aq)”
on the product side.
 When an ionic solid dissolves in water, it

breaks into its constituent ions. This is
called a dissociation reaction. These
compounds conduct electric current and
are electrolytes.
NaCl(aq)  Na  (aq)  Cl  (aq)

 Not all compounds dissolve in water.
 Solubility varies from compound to compound.
Soluble ionic
compounds
dissociate. Most molecular
Ions are
compounds stay
solvated
associated in water.
Types of Reaction in Aqueous Solutions
 Precipitation Reactions
 Acid –Base
 Reduction –Oxidation (Redox)
Precipitation Reaction
 Precipitates are called insoluble – they do
not dissolve in solution
 Precipitation of an insoluble solid
 Mix a solution of nickel(II) chloride with one of
sodium hydroxide
 A solid forms: Ni(OH)2 (s)
Soluble species
 All ammonium and group 1A (Na+, K+,…. and NH4+ salts)
 All nitrates (NO3-)
 Most chlorides, bromides and iodides
 (exceptions: AgX, Hg2X2, and PbX2 ; X = Cl-, Br-, I-).
 Most sulfates (SO42-)
 (exceptions: CaSO4, SrSO4, BaSO4, Ag2SO4, PbSO4, and Hg2SO4)
 All chlorates (ClO3-)
 All perchlorates (ClO4-)
 All acetates (CH3COO-)
(a) Nitrates (b) Hydroxides
(soluble) (insoluble)
AgNO3 Cu(NO3)2 Cu(OH)2 AgOH
(c) Sulfides
CdS Sb2S3 PbS (NH4)2S

soluble
insoluble
 precipitate
 an insoluble ionic compound
 AgNO3(aq) + KCl(aq) → KNO3(aq) + AgCl(s)
When ionic solutions mix, a precipitate may
form:
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)
Not all ions react

KNO3(aq) + NaCl(aq) No reaction
A reaction occurs if a product is insoluble.
The solubility rules help predict reactions.

Na2SO4(aq) and Ba(NO3)2(aq) are
mixed. Will they react?
Products? Na+ SO42-
Ba2+ NO3-
NaNO3 and BaSO4 . Insoluble?
Yes. BaSO4 – A reaction occurs:
Na2SO4(aq) + Ba(NO3)2(aq) BaSO4(s) + 2 NaNO3(aq)

Soluble ionic compounds fully dissociate:
AgNO3(aq) Ag+(aq) + NO3-(aq)
KCl(aq) K+(aq) + Cl-(aq)
On mixing:
Ag+(aq) + NO3-(aq) + K+(aq) + Cl-(aq)
AgCl(s) + K+(aq) + NO3-(aq)
K+ and NO3- appear on both sides
 NO3- and K+ are spectator ions.
 They are not directly involved in the reaction.
Net ionic equation: Ag+(aq) + Cl-(aq) → AgCl(s)

Net Ionic Equations
General rules:
1. Write a balanced equation.
2. Solubility?
3. Dissociate soluble compounds.
4. Write the complete ionic equation.
5. Cancel ions appearing on both sides
(spectators).
6. Check the charges are balanced.
Net Ionic Equations
Example
Aqueous solutions of (NH4)2S and Hg(NO3)2 react to
give HgS and NH4NO3.
(a) Write the overall balanced equation
(b) Name each compound
(c) Write the net ionic equation
(d) What type of reaction is this?
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS + NH4NO3 not balanced
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS + 2 NH4NO3 balanced
Net Ionic Equations
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS (s) + 2 NH4NO3(aq)
Product Solubility
HgS – insoluble
(All sulfides – except group 1A, 2A and NH4+ salts)
NH4NO3 – soluble
(All ammonium salts; all nitrates)
(b) name each compound
ammonium sulfide mercury(II) sulfide
mercury(II) nitrate ammonium nitrate
Net Ionic Equations
(c) Write a net ionic equation
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS(s) + 2 NH4NO3(aq)
2 NH4+(aq) + S2-(aq) + Hg2+(aq) + 2 NO3-(aq)

→ HgS(s) + 2 NH4+(aq) + 2 NO3-(aq)
S2-(aq) + Hg2+(aq) → HgS(s)
(d) type of reaction?

Precipitation reaction
Net Ionic Equations
 Aqueous chemical reactions can be written
as a molecular equation. The complete
formula for each compound is shown.
 Note, all of the species may not be molecules.
HNO3 (aq) + NH 3 (g) 

 NH 4 NO3 (aq)
Net Ionic Equations
 Dissociation of reactants and products is

emphasized by writing a total ionic equation
H+ (aq) + NO3 (aq) + NH3 (g) 
 NH+4 (aq) + NO3 (aq)
 Note: HNO3 is a strong acid and thus

dissociates completely, while NH3 does not
dissociate
Net Ionic Equations
 Spectator ions are ions uninvolved in the
chemical reaction. When spectator ions
are removed, the result is the net ionic
equation.
 Total ionic equation
H+ (aq) + NO3 (aq) + NH3 (g) 
 NH+4 (aq) + NO3 (aq)
 Net ionic equation
H (aq) + NH 3 (g) 
+
 NH (aq)
+
4
Spectator ion = NO3

 A precipitation reaction is an aqueous
reaction that produces a solid, called a
precipitate.

Pb (aq)  2I (aq) 
2+
 PbI2 (s)
 Net ionic reaction for the precipitation of lead(II)
iodide.
 Precipitation reaction between aqueous solutions of KI and Pb(NO3)2, which are

both colorless.
 The bright yellow solid, PbI2, is produced.
 PbI2 is insoluble as predicted by the solubility guidelines.
 When aqueous sodium carbonate and
barium chloride are combined, the solution
becomes cloudy white with solid barium
carbonate. Write the following equations:
a) molecular
b) total ionic
c) net ionic
Acid- Base Reactions
 Acids are substances that dissolve in water

to produce H+ (or H3O+) ions.
 Examples: HCl, HNO3, H3PO4, HCN
 Bases are substances that dissolve in

water to produce OH– ions.
 Examples: NaOH, Ca(OH)2, NH3
Acids and Bases
 Everyday life includes contact with many
acids and bases
Acids
Increase the concentration of H+ ions in
water.
• Protons (H+) always combine with
water to form H3O+ (hydronium ion).
• Sour tasting.
• Change the color of pigments (indicators)
 Litmus, phenolphthalein…
Strong acids dissociate (>99%) in water (strong
electrolytes).
Weak acids partially dissociate (weak electrolytes).
Acids
Hydrochloric acid (HCl) ≈ 100% dissociated in
H2O
 Very few HCl molecules exist in solution.
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
 HCl is a strong acid
Acetic acid (CH3COOH) is 5% dissociated in H2O.
• 95% remain undissociated
CH3COOH(aq) + H2O(l) H3O+ + CH3COO-(aq)
• Acetic acid is a weak acid
Bases
Increase the concentration of OH- (hydroxide
ion) in water. Bases:
• Counteract an acid (neutralize an acid).
• Change an indicator’s color (phenolphthalein…).
• Have a bitter taste.
• Feel slippery.
Bases can be “strong” or “weak”.
H2O
NaOH(s) Na+(aq) + OH-(aq) strong
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) weak

Common Acids and Bases
Strong Acid Strong Base
HCl Hydrochloric acid LiOH Lithium hydroxide
HBr Hydrobromic acid NaOH Sodium hydroxide
HI Hydroiodic acid KOH Potassium hydroxide
HNO3 Nitric acid Ca(OH)2 Calcium hydroxide
H2SO4 Sulfuric acid Ba(OH)2 Barium hydroxide
HClO4 Perchloric acid Sr(OH)2 Strontium hydroxide
Weak Acid Weak Base

HF Hydrofluoric acid NH3 Ammonia
H3PO4 Phosphoric acid CH3NH2 Methylamine
CH3COOH Acetic acid
H2CO3 Carbonic acid
HCN Hydrocyanic acid
HCOOH Formic acid
C6H5COOH Benzoic acid
Neutralization Reactions
acid + base  salt + water.
salt = ionic compound made from an acid anion and
base cation.
HX(aq) + MOH(aq) MX(aq) + H2O(l)
HBr(aq) + KOH(aq) KBr(aq) + H2O(l)
H3PO4(aq) + 3 NaOH(aq) Na3PO4(aq) + 3 H2O(l)
Neutralizations are exchange reactions.

Net Ionic Equations for Acid-Base Reactions
Strong Acid + Strong Base
Overall: HX + MOH → MX + H2O
Full ionic:
H+(aq) + X-(aq) + M+(aq) + OH-(aq) →
M+(aq) + X-(aq) + H2O(l)
net ionic: H+(aq) + OH-(aq) → H2O(l)

Net Ionic Equations for Acid-Base Reactions
Weak Acid + Strong Base
Similar: HA + MOH → MA + H2O
but the weak-acid remains undissociated:
Full ionic
HA(aq) + M+(aq) + OH-(aq) →
M+(aq) + A-(aq) + H2O(l)
Net ionic: HA(aq) + OH-(aq) → A-(aq) + H2O(l)

Metal carbonate/acid exchange Carbonic acid
(unstable)
Overall:
CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + H2CO3(aq)
Tums®
H2CO3(aq) → H2O(l) + CO2(g)
often written:
CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g)
Net ionic:
CaCO3(s) + 2 H+(aq) → Ca2+(aq) + H2O(l) + CO2(g)
Metal hydrogen carbonate/acid exchange
Overall:
NaHCO3(aq) + HCl(aq)→ NaCl(aq) + H2O(l) + CO2(g)
Alka-Seltzer ®
Net ionic
HCO3-(aq) + H+(aq) →
H2O(l) + CO2(g)
Metal sulfite/acid exchange Sulfurous acid
(unstable)
Similar. Overall:
Na2SO3(aq) + 2 HCl(aq) → 2 NaCl(aq) + H2SO3(aq)
H2SO3(aq) → H2O(l) + SO2(g)
or
Na2SO3(aq) + 2 HCl(aq) →
2 NaCl(aq) + H2O(l) +SO2(g)
net ionic: SO32-(aq) + 2 H+(aq) → H2O(l) + SO2(g)

Metal sulfide/acid exchange

Overall:
Na2S(aq) + 2 HCl(aq) → 2 NaCl(aq) + H2S(g)
net ionic: S2-(aq) + 2 H+(aq) → H2S(g)

 Many metals will react with acids,

producing hydrogen gas
 When aqueous solutions of acetic acid and

potassium hydroxide are combined, a
neutralization reaction will occur. Write the
following equations:
a) molecular
b) total ionic
c) net ionic
THEORIES OF ACIDS AND BASES
 Arrhenius Theory
 Brønsted-Lowry Concept
 Lewis Theory
Arrhenius Definition
Arrhenius: any substance which ionizes in
water to produce:
• Protons is an Acid
• Hydroxide ions is a Base
Better version of the Arrhenius definition:

Acid: Hydronium ions (H3O+) in water are acidic.
Base: Hydroxide ions (OH-) in water are basic.
So, why is NH3(aq) basic?
Brønsted-Lowry Concept
An alternative definition:
Brønsted-Lowry Acid = Proton donor
Brønsted-Lowry Base = Proton acceptor
Works for non-aqueous solutions and explains why
NH3 is basic:
NH3(g) + H2O(l) NH4+(aq) + OH-(aq)
Base: Acid:
H+ acceptor H+ donor
Brønsted-Lowry Concept
Strong acids and bases almost completely
ionize.
HNO (aq) + H O(l) H O+(aq) + NO -(aq)
3 2 3 3
Weak acids and bases do not fully ionize.

HF(aq) + H2O(l) H3O+(aq) + F-(aq)
H2O(l) + NH3(aq) NH4+(aq) + OH-(aq)
Acid: Base: Acid: Base:
H+ donor H+ acceptor H+ donor H+ acceptor
Note: the products are a new acid and base pair.

Water’s Role as Acid or Base
Water acts as a base when an acid dissolves in
water:
HBr(aq) + H2O(l) H3O+(aq) + Br-(aq)
acid base acid base
But water acts as an acid for some bases:
H2O(l) + NH3(aq) NH4+(aq) + OH-(aq)

acid base acid base
Water is amphiprotic - it can donate or accept a
proton (act as acid or base).
Conjugate Acid-Base Pairs
Molecules or ions related by the loss/gain of one
H+. Conjugate Acid Conjugate Base
H3O+ H2O
CH3COOH CH3COO-
NH4+ donate H+ NH3
H2SO4 HSO4-
HSO4- accept H+ SO42-
HCl Cl-
NH4+ and NH2- are not conjugate

(conversion requires 2 H+)
Conjugate Acid-Base Pairs
Identify the base conjugate to HF(aq) and the acid
conjugate to HCO3-(aq)
HF H+ + F-
Acid: Conjugate
H+ donor Base
HCO3- + H+ H2CO3
Base: Conjugate
H+ acceptor Acid
( CO32- is the base conjugate to HCO3- )

Relative Strength of Acids & Bases
Strong acids are better H+ donors than weak
acids
Strong bases are better H+ acceptors than weak
bases
 Strong acids have weak conjugate bases.
 Weak acids have strong conjugate bases.
Strong acid + H2O H3O+ + conjugate base
Fully ionized, reverse reaction essentially does not occur.
The conjugate base is weak.
Weak acid + H2O H3O+ + conjugate base
Weakly ionized, reverse reaction readily occurs.

The conjugate base is strong.
Relative Strength of Acids & Bases
Conjugate acid Conjugate base
H2SO4 HSO4-
HBr Br- extremely
stong acids
weak bases
HCl Cl-
HNO3 NO3-
Base strength increasing

H3O+ H2O
Acid strength increasing
H2SO3 HSO3-
HSO4- SO42-
H3PO4 H2PO4-
HF F-
CH3COOH CH3COO-
H2S HS-
H2PO4- HPO42-
NH4+ NH3
HCO3- CO32-
H2O OH-
OH- O2-
H2 extremely H- strong base
CH4 weak acids CH3 -
Autoionization of Water
Two water molecules can react to form ions.
Autoionization occurs:
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
Base Acid Acid Base
Heavily reactant favored.

Only a very small fraction is ionized:
Kw = [ H3O+ ] [ OH- ] [H2O]2 is
ionization omitted…
constant for
water
= (1.0 x 10-7)(1.0 x 10-7)
= 1.0 x 10-14 (at 25°C)
Ionization Constant for Water
Kw, like all equilibrium constants, is T-
dependent.
T = 25°C (77°F) is usually used as the standard
T.
T (°C) Kw
10 0.29 x 10-14
15 0.45 x 10-14
20 0.68 x 10-14
25 1.01 x 10-14
30 1.47 x 10-14
50 5.48 x 10-14
H3O+ and OH- are present in all aqueous
solutions.
Neutral solution.
Pure water (@ 25°C): [H3O+] = 10-7 M = [OH-]
• [ H3O+ ] is increased, disturbing the equilibrium:
2 H2O H3O+ + OH-
Acidic solution
If acid is added to water:
• LeChatelier: equilibrium shifts to remove [H3O+] (and [OH-])
• Equilibrium is reestablished: [ H3O+ ] > 10-7 M > [OH-]
• [ H3O+ ][OH-] = Kw = 1.0 x 10-14 at 25°C

Basic solution.
If base is added to water.
 LeChatelier: equilibrium shifts to remove [ OH- ] (and [H3O+])
 New equilibrium: [H3O+] < 10-7 M < [OH-]
 [ H3O+ ][OH-] = Kw = 1.0 x 10-14 at 25°C
Example
Calculate the hydronium and hydroxide ion concentrations at 25°C in a 6.0 M
aqueous sodium hydroxide solution.
Kw = [H3O+][OH-] = 1.0 x 10-14
NaOH (aq) is strong (100% ionized) so [OH-] = 6.0 M.
[H3O+](6.0) = 1.0 x 10-14
[H3O+] = 1.7 x 10-15 M [ OH- ] = 6.0 M
Values of Acid and Base Ionization Constants
• Strong acid Ka are hard to measure

 They are very large, ≈100% ionized.
 Assume they are fully ionized.
• Larger Ka = stronger acid
• Strong base Kb are hard to measure…

• Larger Kb = stronger base
Ka Values for Polyprotic Acids
Phosphoric acid (H3PO4) is weak. It has three acidic
protons:
H+ is harder to remove
Ka decreasing
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4- (aq)
Ka = 7.5 x 10-3
H2PO4-(aq) + H2O(l) H3O+(aq) + HPO42- (aq)
Ka = 6.2 x 10-8
HPO42-(aq) + H2O(l) H3O+(aq) + PO43- (aq)
Ka = 3.6 x 10-13
Molecular Structure and Acid Strength
What makes a strong acid?
 A weak H–A bond, so H+ can be easily removed!
Consider the binary acids HF, HCl, HBr, HI.
larger acid strength

HX Bond Energy (kJ) Ka
smaller bond energy

HF weak acid 566 7 x 10-4
HCl 431 1 x 107
strong acids
HBr 366 1 x 108

HI 299 1 x 1010
Lewis Acids and Bases
A more general acid-base definition:
A Lewis acid accepts a pair of e- to form a bond.
A Lewis base donates a pair of e- to form a bond.
A + A B
..
B
Acid Base Coordinate

e- pair acceptor e- pair donor covalent bond
Coordinate covalent bond: a shared e- pair, with both e- donated by the same atom.
H H
Examples:
H + O H O H
Lewis acid Lewis base H
H+ + H2O H3O+
F H F H
F B + N H F B N H
F H F H
Lewis acid Lewis base
Positive Metal Ions as Lewis Acids
Metal ions can act as Lewis acids. They have:
 Missing e-
 Empty valence orbitals
 Metal atom + Lewis base → complex ion
Ag+ (aq) + 2 :NH3 (aq) [H3N:Ag:NH3]+ (aq)
Hydroxide ions are Lewis bases δ- δ+

 O is e- rich (has large electronegativity) -
:
:O–H
 Can easily donate an e- pair to a bond
:
Positive Metal Ions as Lewis Acids
Many metal hydroxides are amphoteric – they react
with acids and bases.
Aluminum hydroxide can act as a Lewis acid:

Al(OH)3(s) + OH-(aq) [Al(OH)4]-(aq)
or as a Brønsted-Lowry base:
Al(OH)3(s) + 3 H3O+(aq) Al3+(aq) + 6 H2O(l)
Predict if the following are Lewis acids or Lewis bases.
PH3 BCl3 Cr3+ CO
base acid acid base
(base = e--pair donor; acid = e--pair acceptor)
H Cl
P H Cl B
C O
H Cl
Acid-Base Titrations
 Commonly used to determine the
concentration of a dissolved species or its
percentage in a mixture
 Titration
 Measuring the volume of a standard solution
(known concentration) needed to react with a
measured quantity of a sample
Titrations
 Titrant (in the buret)
 Know concentration
 Know volume
 Analyte (in the Erlenmeyer flask)
 Know volume or mass
 Determine concentration or mass percent by
reacting with the titrant
Analyzing for Acetic Acid
 HC2H3O2 (aq) + OH- (aq) ⇌ C2H3O2- (aq) + H2O
 The objective is to determine when the reaction is
complete
 When the number of moles of acid equals the
number of moles of OH-, the equivalence point has
been reached
 Equivalence point is where the number of moles of
acid equals the number of moles of base
 The endpoint is indicated by a color change in the
acid-base indicator
An Acid- Base Titration
An Acid- Base Titration
Titrant: Base
of known
concentration
Buret = volumetric glassware used for
titrations.
Slowly add standard solution.
End point: indicator changes

color.
Determine Vtitrant added.

Unknown acid + phenolphthalein
(colorless in acid)… …turns pink
in base
Solution Preparation
Solutions are prepared either by:
1. Diluting a more concentrated solution.

or…
2. Dissolving a measured amount of solute
and diluting to a fixed volume.
Dilution of Solution
 Dilution is the process in which solvent is
added to a solution to decrease the
concentration of the solution.
 The number of moles of solute is the same
before and after dilution.
 Since the number of moles of solute equals the
product of molarity and volume (M  V), we can
M V = M V
write the following equation, where the subscripts
denote initiali and final
i values.
f f
MconcVconc = MdilVdil
Example
Commercial concentrated sulfuric acid is 17.8 M.
If 75.0 mL of this acid is diluted to 1.00 L, what is the
final concentration of the acid?
Mconc = 17.8 M Vconc = 75.0 mL
Mdil = ? Vdil = 1000. mL
Mdil = MconcVconc = 17.8 M x 75.0 mL = 1.34 M
Vdil 1000. mL
 A chemist requires 1.5 M hydrochloric acid,
HCl, for a series of reactions. The only
solution available is 6.0 M HCl. What
volume of 6.0 M HCl must be diluted to
obtain 5.0 L of 1.5 M HCl?
Solution Preparation from Pure Solute
Prepare a 0.5000 M solution of potassium

permanganate in a 250.0 mL volumetric flask.
Mass of KMnO4 required
nKMnO4 = [KMnO4] x V
= 0.5000 M x 0.2500 L (M ≡ mol/L)
= 0.1250 mol KMnO4
Mass of KMnO4 = 0.1250 mol x 158.03 g/mol
= 19.75 g
Solution Preparation from Pure Solute
Weigh exactly 19.75 g of pure
KMnO4
Transfer it to a volumetric flask.
• Rinse all the solid from the weighing

dish into the flask.
• Fill the flask ≈ ⅓ full.
• Swirl to dissolve the solid.
• Fill the flask to the mark on the neck.

• Shake to thoroughly mix.
Molarity and Reactions in Aqueous Solution
nA = [ A ] x V
[product] = nproduct / (total volume).

Calculations Involving Molarity
 Example 11-1: If 100.0 mL of 1.00 M NaOH
and 100.0 mL of 0.500 M H2SO4 solutions
are mixed, what will the concentration of
the resulting solution be?
 What is the balanced reaction?
 It is very important that we always use a
balanced chemical reaction when doing
stoichiometric calculations.
75
2 NaOH + H2SO4  Na 2SO4  2 H2O

Reaction
Ratio: 2 mmol 1 mmol 1 mmol 2 mmol
Before
Reaction: 100 mmol 50 mmol 0 mmol 0 mmol
After
 What is the total volume of solution?
100.0 mL + 100.0 mL = 200.0 mL
 What is the sodium sulfate amount, in
mmol?
50.0 mmol
 What is the molarity of the solution?
M = 50 mmol/200 mL = 0.250 M Na2SO4
77
 Example 11-2: If 130.0 mL of 1.00 M KOH
and 100.0 mL of 0.500 M H2SO4 solutions
are mixed, what will be the concentration of
KOH and K2SO4 in the resulting solution?
 What is the balanced reaction?
78
2 KOH + H 2SO 4  K 2SO 4 + 2 H 2 O
Reaction
Ratio: 2 mmol 1 mmol 1 mmol 2 mmol
Before
After
79
 What is the total volume of solution?
130.0 mL + 100.0 mL = 230.0 mL
 What are the potassium hydroxide and
potassium sulfate amounts?
30.0 mmol & 50.0 mmol
 What is the molarity of the solution?
M = 30.0 mmol/230.0 mL = 0.130 M KOH
M = 50.0 mmol/230.0 mL = 0.217 M K2SO4
80
 Example 11-3: What volume of 0.750 M
NaOH solution would be required to
completely neutralize 100 mL of 0.250 M
H3PO4?
You do it!
81
3 NaOH + H 3PO 4  Na 3PO 4 + 3 H 2O

0.250 mol H 3PO 4
? L NaOH = 0.100 L H 3PO 4  
1 L H 3PO 4
3 mol NaOH 1 L NaOH
  0.100 L NaOH
1 mol H 3PO 4 0.750 mol NaOH
82
Oxidation-Reduction Reactions
Oxidation
Originally: add oxygen.
2 Cu(s) + O2(g) 2 CuO(s)
2 CO(g) + O2(g) 2 CO2(g)
Cu and CO are oxidized. O2 is the oxidizing agent for both.
Reduction
Originally: reduce ore to metal; reverse of oxidation.
CuO(s) + H2(g) Cu(s) + H2O
SnO2(s) + 2 C(s) Sn(s) + 2 CO(g)
CuO and SnO2 are reduced. H2 and C are the reducing agents
(note: H2 is oxidized, so CuO is an oxidizing agent)

In all cases:
 If something is oxidized, something must be reduced.
• Oxidation-reduction = redox.
• Redox reactions move e-.
+2 e-
2 Ag+(aq) + Cu(s) 2 Ag(s) + Cu2+(aq)
-2 e-
Here:
• Cu changes to Cu2+.
• Cu loses 2 e-; each Ag+ gains one e-
• Ag+ is reduced (ore turned to metal)
• Gain of e- = reduction (so, loss of e- = oxidation)
Redox Reactions and Electron Transfer
Loss of electrons is oxidation
Gain of electrons is reduction
Leo says ger
Oxidation is loss
Reduction is gain
Oil rig
Redox Reactions and Electron Transfer
e-
M X
M loses electron(s) X gains electron(s)
M is oxidized X is reduced
M is a reducing agent X is an oxidizing agent
Common Oxidizing and Reducing Agents
Oxidizing Agent Reaction Product
O2 (oxygen) O2- (oxide ion)
H2O2 (hydrogen peroxide) H2O(l)
F2, Cl2, Br2, I2 (halogen) F-, Cl-, Br-, I- (halide ion)
HNO3 (nitric acid) nitrogen oxides (NO, NO2..)
Cr2O7- (dichromate ion) Cr3+ (chromium(III) ion)
MnO4- (permanganate ion) Mn2+ (manganese(II) ion)
Reducing Agent Reaction Product
H2 (hydrogen) H+ or H2O
C CO and CO2
M (metal: Na, K, Fe…..) Mn+ (Na+, K+, Fe3+…..)
Oxidation Numbers & Redox Reactions
Oxidation number
Compares the charge of an uncombined atom
with its actual or relative charge in a
compound.
General rules:
 Pure element = 0.
 Monatomic ion = charge of ion.

 Some elements have the same oxidation number in
almost all their compounds…
 The sum of the oxidation numbers of all atoms in any
species = the charge of the species.
Element Ox. No. Exceptions?
F −1 None
Cl, Br, I −1 Interhalogens (various values)
H +1 Metal hydrides = -1
(e.g. NaH, MgH2)
O −2 Metal peroxides = -1
(MO2)
Halogen oxides (various values)
(OXn)
Find the oxidation number for all elements in

SO32-
O = -2 ( not a peroxide, not bonded to halogen)
Sulfur?
Sum of the oxidation numbers = charge = -2
(ox. no. for S) + 3(ox. no. for O) = -2
(ox. no. for S) + 3(-2) = -2
(ox. no. for S) – 6 = -2
Sulfur = +4
Oxidation Numbers
Assign oxidation numbers to each element in the
following compounds:
 NaNO3
 Na = +1
 O = -2
 N = +5
 Calculate
 +1 + 3(-2) + x = 0
 x = +5
91
Oxidation Numbers
 K2Sn(OH)6
 K = +1
 O = -2
 H = +1
 Sn = +5
 Calculate
 2(+1) + 6(-2) + 6(+1) + x = 0
 x = +5
92
Oxidation Numbers
 H3PO4
You do it!
 H = +1
 O = -2
 P = +5
93
Oxidation Numbers
 HCO3-
 O = -2
 H = +1
 C = +4
 Calculate
 +1 + 3(-2) + x = -1
 x = +4
94
Oxidation Numbers
 Cr2O72-
You do it!
 O = -2
 Cr = +6
95
Compound Known Unknown
SO2 O = -2 S = +4
SO42- O = -2 S = +6
NH4+ H = +1 N = -3
NO2- O = -2 N = +3
NO3- O = -2 N = +5
OF2 F = -1 O = +2
ClF5 F = -1 Cl = +5
KMnO4 K = +1 O = -2 Mn = +7
H2O2 H = +1 O = -1
Ox. numbers always change during redox
reactions
Increase ox. number = Oxidation
Decrease ox. number = Reduction
If an element reacts to form a compound, it is a redox
reaction.
Oxidation and reduction must both occur.

S8(s) + 8 O2(g) 8 SO2(g)
S : 0 → +4 (oxidized: added O; lost e-; increased ox. no.)
O : 0 → -2 (reduced: lost O; gained e-; decreased ox. no.)
A more complex example:
0 +1 +5 −2
Cu(s) + 4 H+(aq) + 2 NO3-(aq)
Cu2+ (aq) + 2 NO2 (g) + 2 H2O(l)
+2 +4 −2 +1 −2
Cu is oxidized (ox. no. ↑; loss of e-).
H is unchanged.
O is unchanged.
N is reduced (ox. no. ↓; gain of e-).
Exchange reactions are not redox

– no change in oxidation state occurs.
e.g.
+1 +1 −1 +1 +1 −1
AgNO3(aq) + KCl(aq)  KNO3(aq) + AgCl (s)
NO3-: N is in a +5, and O is in a -2 ox. state.

Write and balance the formula unit, total ionic, and net
ionic equations for the oxidation of sulfurous acid to
sulfuric acid by oxygen in acidic aqueous solution.
 Formula unit equation
2 H 2SO 3aq   O2g   2 H 2SO 4aq 

 Total ionic equation
You do it!
 2
2 H 2SO 3aq   O2g   4 H (aq)  2 SO 4(aq)100
 Net ionic equation
You do it!
 2
2 H 2SO 3aq   O2g   4 H (aq)  2 SO 4(aq)
 Which species are oxidized and reduced?

 Identify the oxidizing and reducing agents.
You do it!
101
 H2SO3 is oxidized.
 The oxidation state of S in H2SO3 is +4.
 In SO42-, S has an oxidation state of +6.
 O2 is reduced.
 Oxidation state of O in O2 is 0
 In SO42-, O has an oxidation state of –2.
 H2SO3 is reducing agent.
 O2 is oxidizing agent.
102
Redox Titrations
 Redox reactions can be used to analyze an unknown in
the same way as is done with acid-base reactions
Stoichiometry of Redox Reactions
 Just as we have done stoichiometry
with acid-base reactions, it can also
be done with redox reactions.
 Example : What volume of 0.200 M
KMnO4 is required to oxidize 35.0
mL of 0.150 M HCl? The balanced
reaction is:
2 KMnO 4  16 HCl  2 KCl + 2 MnCl 2  5 Cl2  8 H2O
You do it!
104
35 mL HCl0150
. M HCl  5.25 mmol HCl
 2 mmol KMnO 4 
5.25 mmol HCl   0.656 mmol KMnO 4
16 mmol HCl 
 1 mL 
0.656 mmol KMnO 4    3.28 mL
 0.200 mmol KMnO 4 
105
 Example : A volume of 40.0 mL of iron
(II) sulfate is oxidized to iron (III) by
20.0 mL of 0.100 M potassium
dichromate solution. What is the
concentration of the iron (II) sulfate
solution? The balanced equation is:
2
6 Fe  Cr2O7  14 H +  6 Fe3+  2 Cr3+  7 H2O
2+
You do it!
106
20.0 mL 0.100 M Cr2O7 2

  2.00 mmol Cr O
2 7
2
  
2+
6 mmol Fe
2.00 mmol Cr2 O 7  
2
2 
 12.0 mmol Fe 2+
 1 mmol Cr2 O 7 
12.0 mmol Fe2+
 0.300 M Fe 2+
40.0 mL
107
 Many medicines are
deliberately made as
conjugate acids or
bases so that they
become active
ingredients after
passage through the
stomach.
108
Scope
1. Types of Reactions in Aqueous Solutions
 Precipitation reactions, Acid-Base, Redox
 Net Ionic Equation
 Dilution of Solution
2. Theories of Acids and Bases
3. Strengths of Acids
4. Acid- Base Reaction/ Titration
5. Redox reactions
109
CHM12-3
Lecture Unit 4
Reactions in Aqueous Solutions
110
CHM12-3
Lecture Unit 5
 BASIC CHEMICAL AND IONIC EQUILIBRIA
1
Unit Goals
1. Chemical Equilibrium Basic Concepts

2. The Equilibrium Constant and Reaction Quotient
3. Le Chatelier‟s Principle
4. Partial Pressures and Kc –Kp Relationship
5. Ionic Equilibria Basic Concepts
6. The pH and pOH scales
7. Ionization constants for Acids and Bases
8. Solubility Product Principle
2
Basic Concepts
 Reversible reactions do not go to completion.

 They can occur in either direction
 Symbolically, this is represented as:
cC +dD
a Ag  + b Bg   g  g 
3
Basic Concepts
 Chemical equilibrium exists when two

opposing reactions occur simultaneously at
the same rate.
 A chemical equilibrium is a reversible reaction that
the forward reaction rate is equal to the reverse
reaction rate.
 Chemical equilibria are dynamic equilibria.
 Molecules are continually reacting, even though
the overall composition of the reaction mixture
does not change.
4
Basic Concepts
 Graphically, this is a representation of the
rates for the forward and reverse reactions
for this general reaction.
cC +dD
a Ag  + b Bg   g  g 
5
Basic Concepts
 One of the fundamental ideas of chemical

equilibrium is that equilibrium can be
established from either the forward or reverse
direction.
6
The Equilibrium Constant
 For a simple one-step mechanism reversible

reaction such as:

A(g)  B(g)  C(g)  D(g)
 The rates of the forward and reverse reactions
can be represented as:
Rate f  k f A B which represents the forward rate.
Rate r  k r CD which represents the reverse rate.
7
 When system is at equilibrium:

Ratef = Rater
Substitute for the rate relationsh ip to give :
k f A B  k r CD
which rearranges to
k f CD

k r A B
8
 Because the ratio of two constants is a

constant we can define a new constant as
follows :
kf
 Kc and
kr
Kc 
 C D
A  B
9
 Similarly, for the general reaction:


a A(g)  b B(g)  c C(g)  d D(g)
we can define a constant
Kc 
C D
c d
 products
A B
a b  reactants
This expression is valid for all reactions.

10
 Kc is the equilibrium constant .
 Kc is defined for a reversible reaction at a
given temperature as the product of the
equilibrium concentrations (in M) of the
products, each raised to a power equal to its
stoichiometric coefficient in the balanced
equation, divided by the product of the
equilibrium concentrations (in M) of the
reactants, each raised to a power equal to its
stoichiometric coefficient in the balanced
equation. 11
 Example 17-1: Write equilibrium constant

expressions for the following reactions at
500oC. All reactants and products are gases
at 500oC.

PCl5  PCl3  Cl2
Kc 
PCl3 Cl2 
PCl5  12

H 2 + I 2  2 HI
You do it!
13

H 2 + I 2  2 HI
Kc 
HI 
2
H 2 I 2 
14

4 NH3 + 5 O 2  4 NO + 6 H 2O
You do it!
15

4 NH3 + 5 O 2  4 NO + 6 H 2O
Kc =
NO H 2O
4 6
NH3  O 2 
4 5
16
 Equilibrium constants are dimensionless

because they actually involve a
thermodynamic quantity called activity.
 Activities are directly related to molarity
17
 Example 17-2: One liter of equilibrium mixture from the

following system at a high temperature was found to
contain 0.172 mole of phosphorus trichloride, 0.086 mole
of chlorine, and 0.028 mole of phosphorus pentachloride.
Calculate Kc for the reaction.

 Equil []‟s 0.028 M 0.172 M 0.086 M
You do it!
18
Kc 
PCl3 Cl2 
PCl5 
Kc 
0.1720.086
0.028
K c  0.53
19
 Example 17-3: The decomposition of PCl5

was studied at another temperature. One
mole of PCl5 was introduced into an
evacuated 1.00 liter container. The system
was allowed to reach equilibrium at the new
temperature. At equilibrium 0.60 mole of
PCl3 was present in the container. Calculate
the equilibrium constant at this temperature.
20

PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0
21

PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
22

PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
Equilibriu m 0.40 M 0.60 M 0.60 M
23

PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
K '

0.60 0.60 
 0.90 at another T
c
0.40 24
 Example 17-4: At a given temperature 0.80

mole of N2 and 0.90 mole of H2 were placed
in an evacuated 1.00-liter container. At
equilibrium 0.20 mole of NH3 was present.
Calculate Kc for the reaction.
You do it!
25

N 2(g) + 3 H 2(g)  2 NH3(g)
Initial 0.80 M 0.90 M 0
Change - 0.10 M - 0.30 M + 0.20 M
Kc 
NH3 
2

0.20 
2
 0.26
N 2 H 2  0.700.60
3 3
26
Variation of Kc with the
Form of the Balanced Equation
 The value of Kc depends upon how the balanced
equation is written.
 From example 17-2 we have this reaction:

 This reaction has a Kc=[PCl3][Cl2]/[PCl5]=0.53
27
 Example 17-5: Calculate the equilibrium constant
for the reverse reaction by two methods, i.e, the
equilibrium constant for this reaction.

PCl3  Cl2  PCl5
Equil. []‟s 0.172 M 0.086 M 0.028 M
The concentrations are from Example 17-2.
28
Kc 
'  PCl5 

 0.028
 1.9
 PCl3 Cl2  0.1720.086
Kc  1 ' or '
Kc  1 K  10.53  1.9
Kc c
 Large equilibrium constants indicate that most of
the reactants are converted to products.
 Small equilibrium constants indicate that only
small amounts of products are formed.
29
The Reaction Quotient
 The mass action expression or reaction quotient
has the symbol Q.
 Q has the same form as Kc
 The major difference between Q and Kc is that
the concentrations used in Q are not
necessarily equilibrium values.
For this general reaction :
aA + bB  cC + dD
Q
C D
c d
A B
a b
30
 Why do we need another “equilibrium

constant” that does not use equilibrium
concentrations?
 Q will help us predict how the equilibrium will
respond to an applied stress.
 To make this prediction we compare Q with
Kc.
31
When :
Q = K c The system is at equilibriu m.
Q  K c The reaction occurs to the left to a greater extent.
Q  K c The reaction occurs to the right to a greater extent.
To help understand this think of Q and K c as fractions.
32
 Example 17-6: The equilibrium constant for the
following reaction is 49 at 450oC. If 0.22 mole of
I2, 0.22 mole of H2, and 0.66 mole of HI were put
into an evacuated 1.00-liter container, would the
system be at equilibrium? If not, what must
occur to establish equilibrium?
33
The concentrat ions given in the problem
are not necessaril y equilibriu m []' s.
We can calculate Q.
 2 HI
H 2(g)  I 2(g)  (g)
0.22 M 0.22 M 0.66 M
Q=
HI 
2

0.66
2
 9.0
H 2 I 2  0.220.22
Q  9.0 but K c  49
Q < Kc
34
Uses of the Equilibrium Constant, Kc
 Example 17-7: The equilibrium constant, Kc, is

3.00 for the following reaction at a given
temperature. If 1.00 mole of SO2 and 1.00 mole
of NO2 are put into an evacuated 2.00 L
container and allowed to reach equilibrium, what
will be the concentration of each compound at
equilibrium?
SO2(g)  NO2(g) 
 SO3(g)  NO(g)
35
SO 2(g)  NO2(g) 
 SO3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
36
SO 2(g)  NO2(g) 
 SO3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
37
SO 2(g)  NO2(g) 
 SO 3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Equilibriu m 0.500  x M 0.500  x M xM xM
38
SO 2(g)  NO2(g) 
 SO 3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Kc 
SO3 NO  3.00  x x 
SO 2 NO2  0.500  x 0.500  x 
This equation is a perfect square .
We can take the of both sidesof the equation.
39
SO 2(g)  NO2(g) 
 SO 3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Kc 
SO 3 NO
 3.00 
 x  x 
SO 2 NO2  0.500  x 0.500  x 
This equation is a perfect square.
We can take the of both sides.
x
1.73 =
0.500  x
0.865 - 1.73 x  x; 0.865  2.73 x; x  0.865
2.73
x  0.316M  SO 3   NO
0.500  x M  0.184M  SO 2   NO2 
40
 Example 17-8: The equilibrium constant is 49

for the following reaction at 450oC. If 1.00
mole of HI is put into an evacuated 1.00-liter
container and allowed to reach equilibrium,
what will be the equilibrium concentration of
each substance?

H 2(g) + I 2(g)  2 HI (g)
You do it! 41
 2 HI
H 2(g) + I 2(g)  (g)
Initial 0 0 1.00M
Change + xM + xM - 2x M
Equilibriu m xM xM 1.00 - 2 x  M
Kc =
HI 
2
= 49 =
1.00 - 2 x 
2
H 2 I 2  x x 
K = 7.0 =
1.00 - 2 x 
c
x
7.0 x  1.00  2 x; 9 x  1.00; x  0.11 M
H 2   I 2   xM  0.11 M
HI   1.00  2 x M  0.78 M
42
Le Chatelier’s Principle
 LeChatelier‟s Principle - If a change of conditions

(stress) is applied to a system in equilibrium, the
system responds in the way that best tends to
reduce the stress in reaching a new state of
equilibrium.
 We first encountered LeChatelier‟s Principle in Chapter
14.
 Some possible stresses to a system at
equilibrium are:
1. Changes in concentration of reactants or products.
2. Changes in pressure or volume (for gaseous reactions)
3. Changes in temperature. 43
 For convenience we may express the amount of

a gas in terms of its partial pressure rather than
its concentration.
 To derive this relationship, we must solve the
ideal gas equation.
44
PV  nRT
n
P   RT
V
n
Because   has the units mol/L,
V
P = []RT
Thus at constant T, the partial pressure of a gas
is directly proportion al to its concentrat ion.
45
1 Changes in Concentration of Reactants and/or Products

• Also true for changes in pressure for reactions involving gases.
 Look at the following system at equilibrium at 450oC.
 2 HI
H2  I2  g 
Kc 
HI 
 49
2
H 2 I 2 
46

 2 HI
H 2  I2  g 
Kc 
HI 
2
 49
H 2 I 2 
If some H 2 is added, Q < K c .
This favors the forward reaction.
Equilbrium will shift to the right or product side. 47

 2 HI
H 2  I2  g 
Kc 
HI 
2
 49
H 2 I 2 
If we remove some H 2 , Q > K c
This favors the reverse reaction.
Equilbrium will shift to the left, or reactant side. 48
2 Changes in Volume
• (and pressure for reactions involving gases)
 Predict what will happen if the volume of this system at
equilibrium is changed by changing the pressure at

constant temperature:

2 NO2g   N 2O 4g 
Kc =
N 2O 4 
NO2  2
49
N O
2 NO2g   2 4 g 
Kc =
N 2O 4 
NO2 2
If the volume is decreased, which increases the pressure, Q < K c .
This favors product formation or the forward reaction.
The forward reaction produces fewer moles of gas.
50
N O
2 NO2g   2 4 g 
Kc =
N 2O 4 
NO2  2
If the volume is increased, which decreases the pressure, Q > K c .

This favors the reactants or the reverse reaction.
More moles of gas are produced.
51
3 Changing the Reaction Temperature

 Consider the following reaction at equilibrium:
 2 SO + 198 kJ
2 SO 2g  + O 2g   3 g 
Heat is a product of this reaction

Increasing the reaction t emperature stresses the products.
This favors the reverse or reactant reaction.
52
 Introduction of a Catalyst
 Catalysts decrease the activation energy of both the forward and
reverse reaction equally.
 Catalysts do not affect the position of equilibrium.

 The concentrations of the products and reactants will be the
same whether a catalyst is introduced or not.
 Equilibrium will be established faster with a catalyst.
53
54
Partial Pressures and the Equilibrium
Constant
 For gas phase reactions the equilibrium
constants can be expressed in partial pressures
rather than concentrations.
 For gases, the pressure is proportional to the
concentration.
 We can see this by looking at the ideal gas law.
 PV = nRT
 P = nRT/V
 n/V = M
 P= MRT and M = P/RT
55
Constant
 Consider this system at equilibrium at 5000C.
 4 HCl + O
2 Cl2g  + 2 H 2Og   g  2 g 
HCl O 2 
4
PHCl  PO 
4
Kc  and K p 
PCl  PH O 
2
Cl2  H 2O
2 2 2
2
2
2
56
Constant
Kc 
   
PHCl 4 PO2
PHCl  PO 4
  
1 5
    P  P   
RT RT 2 RT
P 2 P 2 2 2 1 4
Cl2 H 2O
RT RT Cl 2 H 2O RT
Kc  K   so for this
1
p RT reaction
-1 1
K c = K p (RT) or K p = K c (RT)
L atm
Must use R  0.0821
mol K
57
Relationship Between Kp and Kc
 From the previous slide we can see that the

relationship between Kp and Kc is:
K p  K c RT  or K c  K p RT 
n  n
n = (# of moles of gaseous products) - (# of moles of gaseous reactants)
58
 Example 17-15: Nitrosyl bromide, NOBr, is

34% dissociated by the following reaction at
25oC, in a vessel in which the total pressure
is 0.25 atmosphere. What is the value of Kp?
2 NOBrg  
 2 NOg  + Br2g 
59
2 NOBrg  
 2 NOg  + Br2g 
Initial [] x atm 0 0
Change - 0.34 x atm + 0.34 x atm + 0.17 x atm
Equilibriu m x - 0.34 x atm 0.34 xatm 0.17 x atm
60
PTot  PNOBr  PNO  PBr2

0.25 atm = x - 0.34 x  atm  0.34 x atm + 0.17 x atm
0.25 atm = 1.17 x atm, thus x = 0.21 atm.
Because NOBr is 34% dissociate d,
it is 66% undissocia ted.
61
PNOBr  x - 0.34 x   0.66 x

PNOBr  0.660.21 atm   0.14 atm
PNO  0.34 x  0.340.21 atm   0.071 atm
PBr2  0.17 x  0.17 0.21 atm   0.036 atm
PNO  PBr
2
  0.071 0.036  9.3 10
2
3
Kp  2
PNOBr 2
0.14 2
62
 The numerical value of Kc for this reaction

can be determined from the relationship of Kp
and Kc.
K p = Kc  RT or Kc = K p  RT
n  n
n = 1
Kc  9.3  10 3
0.08212981
 38
.  10 4
63
 Example 17-16: Kc is 49 for the following

reaction at 450oC. If 1.0 mole of H2 and 1.0 mole
of I2 are allowed to reach equilibrium in a 3.0-liter
vessel,

H 2g   I 2g   2 HI g 
(a) How many moles of I2 remain unreacted at
equilibrium?
You do it!
64
H 2 g    2 HI
I 2 g   g 
Initial 0.33M 0.33M 0
Change -xM -xM + 2x M
Equilibriu m 0.33 - x M 0.33 - x M 2x M
Kc =
HI 
2
 49 
2x
2
 7.0 
2x
H 2 I 2  0.33 - x 2
0.33 - x
9 x = 2.3; x = 0.256 M
[H 2 ]  [I 2 ]  (0.33  x) M  0.074 M
HI   2 x M  0.51M
? mol I 2  3.0 L  0.074 mol L  0.21 mol 65
(b) What are the equilibrium partial pressures of

H2, I2 and HI?
You do it!
66
PH 2  PI2  MRT  0.074 mol L 0.0821 mol  

K 723 K  4.4 atm
L atm
PHI  MRT  0.51 mol L 0.0821 mol  

K 723 K  30 atm
L atm
67
(c) What is the total pressure in the reaction

vessel?
You do it!
68
PTot = PH2  PI2  PHI  4.4  4.4  30 atm = 39 atm
69
Heterogeneous Equlibria
 Heterogeneous equilibria have more than one
phase present.
 For example, a gas and a solid or a liquid and a gas.
CaCO3s  
 CaOs   CO2g  at 500 C o
 How does the equilibrium constant differ for heterogeneous

equilibria?
 Pure solids and liquids have activities of unity.
 Solvents in very dilute solutions have activities that are essentially
unity.
 The Kc and Kp for the reaction shown above are:
K c = [CO 2 ] K p = PCO 2
70
For this reaction :
 H SO
SO 2aq   H 2 O    o
(at 25 C)
2 3aq 
H 2 O   is the solvent.
What are the forms of K c and K p?
You do it!
Kc =
H 2SO3 
K p is undefined
SO 2 
71
 What are Kc and Kp for this reaction?

 2
CaF2s   Ca aq   2 Faq 
1- o
(at 25 C)
You do it!
Kc = Ca  2
F 
 2
K p is undefined
72
 What are Kc and Kp for this reaction?


3 Fes   4 H 2Og   Fe3O4s   4 H 2g  (at 500 C)o
 P 
4
Kc =
 H2 
4
Kp 
H2
 H 2 O P 
4 4
H 2O
73
Evaluation of Equilibrium Constants at
Different Temperatures
 From the value of Ho and K at one
temperature, T1, we can use the van‟t Hoff
equation to estimate the value of K at
another temperature, T2.
K T2 H (T2  T1 )
o
ln 
K T1 R T2 T1
or
K T2 H o
1 1
ln    
K T1 R  T1 T2  74
 Example 17-19: For the reaction in example
17-18, Ho = 114 kJ/mol and Kp = 4.3 x 10-13
at 25oC. Estimate Kp at 250oC.
2 NO2(g)  2 NO(g) + O2(g)
75
Evaluation of Equilibrium Constants
at Different Temperatures
Let T1  298 K and T2  523 K
apply the van' t Hoff equation
76
Evaluation of Equilibrium Constants
at Different Temperatures
Let T1  298 K and T2  523 K
apply the van' t Hoff equation
K T2 (1.14 10 mol )523  298
5 J
ln 
K T1 8.314 J mol K 523 K 298 K 
K T2
ln  19.795
K T1
77
Take the antilog of both sides of equation.
K T2
 e19.80  4.0  108
K T1
Solve for K T2 & substitute the known valu e of K T1
 
K T2  4.0  108 K T1  4.0  108 4.3  10-13 
4
K T2  1.7 10 @ 250 C vs K T1  4.3  10
o -13 o
@ 25 C
The reaction is more product favored at the higher T.
78
Ionic Equilibria Basic Concept
 This details the equilibria of weak acids and
bases.
 We must distinguish weak acids and bases from strong
electrolytes.
 Weak acids and bases ionize or dissociate
partially, much less than 100%.
 In this unit we will see that it is often less than 10%!
 Strong electrolytes ionize or dissociate
completely.
 Strong electrolytes approach 100% dissociation in
aqueous solutions.
79
 There are three classes of strong electrolytes.
1 Strong Water Soluble Acids
Remember the list of strong acids from Chapter 4.
100%  
HNO3( )  H 2O (  )  H 3O (aq)  NO 3(aq)
or
100%  
HNO3( )  H (aq)  NO 3(aq)
80
10 0%  
HNO 3( )  H 2O (  )  H 3O (aq)  NO 3(aq)
or
10 0%  
HNO 3( )  H (aq)  NO 3(aq)
81
2 Strong Water Soluble Bases
The entire list of these bases was also introduced in
Chapter 4.
H 2 O 100% 
KOH(s)   K (aq)  OH -
(aq)
H 2 O 100% 2
Sr(OH) 2(s)   Sr (aq)  2 OH -
(aq)
82
3 Most Water Soluble Salts
The solubility guidelines from Chapter 4 will help you remember
these salts.
H 2 O 100% 
NaCl(s)   Na (aq)  Cl -
(aq)
H 2 O 100% 2 
Ca(NO3 ) 2s    Ca (aq)  2 NO 3(aq)
83
 The calculation of ion concentrations in solutions of

strong electrolytes is easy.
 Example 18-1: Calculate the concentrations of ions
in 0.050 M nitric acid, HNO3.
 
HNO3( )  H 2O(  ) 
 H 3O
100%
(aq)  NO
3(aq)
0.050 M 0.050 M 0.050 M
84
 Example 18-2: Calculate the concentrations of
ions in 0.020 M strontium hydroxide, Sr(OH)2,
solution.
You do it!
2
Sr(OH) 2(s) 
 Sr
H 2O
(aq)  2 OH -
(aq)
0.020M 0.020M 20.020M 

0.040M
85
The Autoionization of Water
 Pure water ionizes very slightly.

 The concentration of the ionized water is less than one-
millionth molar at room temperature.
86
 We can write the autoionization of water as a

dissociation reaction similar to those previously done
in this chapter.
 
H 2O( )  H 2O( )  H3O(aq)  OH(aq)
-
 Because the activity of pure water is 1, the
  
equilibrium constant for this reaction is:

Kc  H 3O +
OH
87
 Experimental measurements have determined that

the concentration of each ion is 1.0 x 10-7 M at 25oC.
 Note that this is at 25oC, not every temperature!
 We can determine the value of Kc from this
information.

Kc  H 3O OH 
+ 
 1.0 x 10 1.0 x 10 
-7 -7
14
 1.0 x10
88
 This particular equilibrium constant is called the ion-

product for water and given the symbol Kw.
 Kw is one of the recurring expressions for the remainder of
this chapter and Chapters 19 and 20.
K w  H 3O  +
OH  
14
 1.0 x10
89
 Example 18-3: Calculate the concentrations of
H3O+ and OH- in 0.050 M HCl.
HCl + H 2 O  H 3O +  Cl
0.050M 0.050M 0.050M
 
Thus the H 3O +  0.050M .
 
The H 3O + and K w will allow us to calculate [OH - ].
90
 Use the [H3O+] and Kw to determine the [OH-].

You do it!
H O OH   1.0 10

3
+  14
OH   H O   5.0 10

14 14
 1.0  10 1.0  10
+ 2
3
OH   2.0 10 M

 13
91
 The increase in [H3O+] from HCl shifts the

equilibrium and decreases the [OH-].
 Remember from Chapter 17, increasing the product
concentration, [H3O+], causes the equilibrium to shift to the
reactant side.
 This will decrease the [OH-] because it is a product!
The [H 3O  ] from HCl is 0.050M
H 2O  H 2O   H O  OH -
3

The [H 3O ] from K w is 2.0 10 M . -13
The overall [H 3O  ]  0.050  2.0 10-13 M  0.050 M .
92
 Now that we know the [H3O+] we can calculate the

[OH-].
You do it!
K w  [H 3O  ][OH-]  110-14
Since [H 3O  ]  0.050 M .
1  10 -14
[OH- ] 
[H 3O  ]
1  10 -14
[OH- ] 
[0.050 M ]
[OH- ]  2.0 10 13 M
93
The pH and pOH scales
 A convenient way to express the acidity and basicity

of a solution is the pH and pOH scales.
 
 The pH of an aqueous solution is defined as:
+
pH = -log H 3O
94
 In general, a lower case p before a symbol is read

as the „negative logarithm of‟ the symbol.
 Thus we can write the following notations.
 
pOH = -log OH -
pAg = -logAg  +
and so forth for other quantities .
95
 If either the [H3O+] or [OH-] is known, the pH and

pOH can be calculated.
 Example 18-4: Calculate the pH of a solution in
which the [H3O+] =0.030 M.
pH = -log H 3O  +

pH   log 3.0 10  2

pH  1.52
96
 Example 18-5: The pH of a solution is 4.597. What

is the concentration of H3O+?
You do it!

pH  -log[H 3O ]
4.597  -log[H 3O  ]

log[H 3O ]  -4.597
[H 3O  ]  10-4.597
[H 3O  ]  2.53 10 5 M
97
 A convenient relationship between pH and pOH may

be derived for all dilute aqueous solutions at 250C.
  14
[H 3O ][OH ]  1.0 10
 Taking the logarithm of both sides of this equation
gives:
 

log H 3O  log OH  14.00  

98
 Multiplying both sides of this equation by -1 gives:
 
- log H 3O   log OH   
  14.00
 Which can be rearranged to this form:
pH  pOH  14.00
99
 Remember these two expressions!!

 They are key to the next three chapters!
H O OH   1.0 10

3
  14
pH  pOH  14.00
100
 The usual range for the pH scale is 0 to 14.
H O   1.0 M to H O   1.0 10

3

3
 14
M
pH  0 to pH  14.00
 And for pOH the scale is also 0 to 14 but
inverted from pH.
 pH = 0 has a pOH = 14 and pH = 14 has a pOH = 0.
OH   1.0 10

 14

M up to OH  1.0M 

pOH  14.00 pOH  0
101
 Example 18-6: Calculate the [H3O+], pH, [OH-], and

pOH for a 0.020 M HNO3 solution.
 Is HNO3 a weak or strong acid?
 What is the [H3O+] ?
HNO 3  H 2 O   H 3O   NO3-
100%
0.020M 0.020 M 0.020M

H O   2.0 10 M
3
 2
pH  -log 2.0 10 M 

2
pH  1.70
102
 Example 18-6: Calculate the [H3O+], pH, [OH-], and

pOH for a 0.020 M HNO3 solution.
  
K w  H 3O  OH   1.0 10 14
OH   H O   2.0 10  5.0 10

14 14
 1.0 10 1.0 10 13
 2
M
3
pOH   log 5.0 10   12.30

13
103
 To help develop familiarity with the pH and pOH scale we can
look at a series of solutions in which [H3O+] varies between 1.0
M and 1.0 x 10-14 M.
[H3O+] [OH-] pH pOH

1.0 M 1.0 x 10-14 M 0.00 14.00
1.0 x 10-3 M 1.0 x 10-11 M 3.00 11.00
1.0 x 10-7 M 1.0 x 10-7 M 7.00 7.00
2.0 x 10-12 M 5.0 x 10-3 M 11.70 2.30
1.0 x 10-14 M 1.0 M 14.00 0.00
104
Ionization Constants for Weak
Monoprotic Acids and Bases
 Let‟s look at the dissolution of acetic acid, a weak
acid, in water as an example.
 The equation for the ionization of acetic acid is:
 
CH3COOH  H 2O  H3O  CH3COO-
 The equilibrium constant for this ionization is

expressed as:
Kc 
H O CH COO 
3

3

CH3COOHH 2O
105
 The water concentration in dilute aqueous solutions
is very high.
 1 L of water contains 55.5 moles of water.
 Thus in dilute aqueous solutions:
H2O  55.5M
106
 The water concentration is many orders of
magnitude greater than the ion concentrations.
 Thus the water concentration is essentially that of
pure water.
 Recall that the activity of pure water is 1.
K H O 
3

3

c 2
CH3COOH
K
3

3

CH3COOH
107
 We can define a new equilibrium constant for weak
acid equilibria that uses the previous definition.
 This equilibrium constant is called the acid ionization
constant.
 The symbol for the ionization constant is Ka.
Ka 
3

 1.8 10
3

5
CH3COOH
for acetic acid
108
 In simplified form the dissociation equation and
acid ionization expression are written as:
 
CH3COOH  H  CH3COO-
Ka 
H CH COO 

3

 1.8 10 5
CH3COOH
109
 The ionization constant values for several acids are
given below.
 Which acid is the strongest?
Acid Formula Ka value
Acetic CH3COOH 1.8 x 10-5
Nitrous HNO2 4.5 x 10-4
Hydrofluoric HF 7.2 x 10-4
Hypochlorous HClO 3.5 x 10-8
Hydrocyanic HCN 4.0 x 10-10
110
 From the above table we see that the order of
increasing acid strength for these weak acids is:
HF > HNO2 > CH3COOH > HClO > HCN
 The order of increasing base strength of the anions
(conjugate bases) of these acids is:
- - - - -
F < NO < CH3COO < ClO < CN
2
111
 Example 18-8: Write the equation for the ionization
of the weak acid HCN and the expression for its
ionization constant.
 
HCN  H  CN -
Ka 
H CN 
 -
 4.0 x 10 -10
HCN 
112
 Example 18-9: In a 0.12 M solution of a weak
monoprotic acid, HY, the acid is 5.0% ionized.
Calculate the ionization constant for the weak acid.
You do it!

HY  H + Y
+ -
Ka 
 H Y 
+ -
 HY
113
 Since the weak acid is 5.0% ionized, it is also 95% unionized.
 Calculate the concentration of all species in solution.
H   Y   0.05(0.12M )  0.0060M
+ 
H   Y   6.0 10 M
+  3
HY   0.95(0.12M )  0.11M
114
 Use the concentrations that were just determined in the
ionization constant expression to get the value of Ka.
Ka 
H Y 
 
HY 
Ka 
6.0 10 6.0 10 
3 3
0.11
K a  3.3 10  4
115
 Example 18-10: The pH of a 0.10 M solution of a
weak monoprotic acid, HA, is found to be 2.97.
What is the value for its ionization constant?
pH = 2.97 so [H+]= 10-pH
H   10
 2.97
H   1.110
 3
M
116
 Use the [H3O+] and the ionization reaction to
determine concentrations of all species.
HA 
 H+  A-

Equil. []'s 0.10 - 1.1  10-3  1.1  10-3 1.1  10-3
 0.10
117
 Calculate the ionization constant from this
information.
Ka 
H A  1.1 10 1.1 10 


 -3 -3
HA  0.10
K a  1.2  10 5
118
 Example 18-11: Calculate the concentrations of the
various species in 0.15 M acetic acid, CH3COOH,
solution.
 It is always a good idea to write down the ionization
reaction and the ionization constant expression.
CH3COOH  H 2 O 
 H 3O   CH 3COO-
Ka 
3

3
-
 1.8 10 5
CH3COOH
119
 Next, combine the basic chemical concepts with
some algebra to solve the problem.
CH3COOH  H 2O 
 H 3O   CH3COO-
Initial [] 0.15M
120
 Next we combine the basic chemical concepts with
some algebra to solve the problem
CH3COOH  H 2O 
 H 3O   CH3COO-
Initial [] 0.15M
Change - xM  xM  xM
121
 Next we combine the basic chemical concepts with
some algebra to solve the problem
 
CH3COOH  H 2O  H 3O  CH3COO-
Initial [] 0.15M
Equilibriu m [] ( 0.15-x)M  xM  xM
122
 Substitute these algebraic quantities into the
ionization expression.
Ka 
H 3 O 
CH
3 COO 

CH 3COOH

 x  x   1.8  10 5
0.15  x 
123
 Solve the algebraic equation, using a simplifying assumption that
is appropriate for all weak acid and base ionizations.
2
x
 1.8 10 5
0.15  x
x 2  0.15  x 1.8 10 5
124
 Solve the algebraic equation, using a simplifying assumption that
is appropriate for all weak acid and base ionizations.
x2
 1.8 10 5
0.15  x
x 2  0.15  x 1.8 10 5
Ka
 10 3 then make this assumption .
If

x is small enough to ignore compared to [].
x  0.151.8 10
2 5
125
 Complete the algebra and solve for the concentrations of the
species.
x 2  2.7 10 6
  
x  1.6 10 3 M  H 3O   CH 3COO 
CH3COOH  0.15  1.6 103 M  0.15M
126
 Note that the properly applied simplifying assumption gives
the same result as solving the quadratic equation does.
 x  x   1.8  10 5
0.15  X 
5 6
x  1.8  10 x  2.7  10
2
0
a b c
b b 2  4ac
x
2a
127
x

 1.8 10 5
  1.8 10 
5 2

 41  2.7 10 6 
21
x  1.6 10 3 and - 1.6 10-3
128
 Let us now calculate the percent ionization for the
0.15 M acetic acid. From Example 18-11, we know
the concentration of CH3COOH that ionizes in this
solution. The percent ionization of acetic acid is
CH3COOHionized
% ionization = 100%
CH3COOHoriginal
3
1.6 10 M
% ionization  100%  1.1%
0.15M
129
 Example 18-12: Calculate the concentrations
of the species in 0.15 M hydrocyanic acid,
HCN, solution.
Ka= 4.0 x 10-10 for HCN
You do it!
130
 H O   CN -
HCN  H 2 O  3
Initial   0.15 M
Change -xM +xM +xM
Equilibriu m 0.15 - x  M xM xM
Ka 
H  CN 



x x   4.0 10 10
HCN  0.15  x
x 2  6.0 10 11
  
x  7.7 10 6 M  H   CN  
HCN   0.15  x  M  0.15 M
131
 The percent ionization of 0.15 M HCN solution is
calculated as in the previous example.
% ionization =
HCN ionized
100%
HCN original
6
7.7 10 M
% ionization  100%  0.0051%
0.15M
132
 Let‟s look at the percent ionization of two weak
acids as a function of their ionization constants.
Examples 18-11 and 18-12 will suffice.
Solution Ka [H+] pH % ionization
0.15 M 1.8 x 10-5 1.6 x 10-3 2.80 1.1
acetic acid
0.15 M 4.0 x 10-10 7.7 x 10-6 5.11 0.0051
HCN
 Note that the [H+] in 0.15 M acetic acid is 210

times greater than for 0.15 M HCN.
133
 All of the calculations and understanding we have at
present can be applied to weak acids and weak
bases!
 One example of a weak base ionization is ammonia
ionizing in water.
134
 All of the calculations and understanding we have at
present can be applied to weak acids and weak
bases!
 Example 18-13: Calculate the concentrations of the
various species in 0.15 M aqueous ammonia.
NH3  H 2 O 
 NH4  OH-
Initial [] 0.15M
135
Monoprotic Acids and
NH  H O 
Bases
 NH  OH  -
3 2 4
Initial [] 0.15M
Kb 
NH OH  

4
-
x x   1.8 10 5
NH3  0.15  x 
The simplifyin g assumption is valid.
x  0.15 thus 0.15 - x  0.15
x x  x x   1.8 105

0.15  x  0.15
x 2  (0.15)1.8 10 5
x 2  2.7 10 6 and x  1.6 10-3 M
NH   OH   1.6 10 M

4
- -3
NH   0.15  1.6 10 M  0.15M

3
-3
136
 The percent ionization for weak bases is calculated
exactly as for weak acids.
NH3 ionized
% ionization  100%
NH3 original
3
1.6 10 M
 100%
0.15M
 1.1%
137
 Example 18-14: The pH of an aqueous
ammonia solution is 11.37. Calculate the
molarity (original concentration) of the
aqueous ammonia solution.
You do it!
138
pH = 11.37
From pH + pOH = 14.00, we can derive the pOH.
pOH = 14.00 - pH  14.00 - 11.37  2.63
OH   10  10  2.3 10
-  pOH  2.63 3
M
NH   2.3 10 M

4
3
139
 Use the ionization equation and some algebra to get
the equilibrium concentration.
 
NH3  H 2O  NH4  OH -
Initial[] xM
Change - 2.3 10-3 + 2.3 10-3 + 2.3 10-3
 
Equilibriu m[] x - 2.3 10-3 M + 2.3 10-3 + 2.3 10-3
140
 Substitute these values into the ionization constant
expression.
Kb 
NH OH 

4

 1.8 10 5
NH3 
1.8 10 5

2.3 10 2.3 10 
3 3
x  2.3 10  3
141
 Examination of the last equation suggests that our
simplifying assumption can be applied.
 In other words (x-2.3x10-3)  x.
 Making this assumption simplifies the calculation.
2.3 10  3 2
 1.8 10 5
x
x  0.30M NH3
142
Solubility Product Constants
 Silver chloride, AgCl,is rather insoluble in water.

 Careful experiments show that if solid AgCl is
placed in pure water and vigorously stirred, a
small amount of the AgCl dissolves in the water.
    
Ag Cl  Ag aq   Claq 
143
 The equilibrium constant expression for this

dissolution is called a solubility product constant.
 Ksp = solubility product constant

K sp  [Ag ][Cl ]  1.8 10 - -10
144
 The solubility product constant, Ksp, for a

compound is the product of the concentrations of
the constituent ions, each raised to the power that
corresponds to the number of ions in one formula
unit of the compound.
 Consider the dissolution of silver sulfide in water.
+ 2-    H 2O
Ag2 S 
100%
 2 +
Ag + S 2-
145
 The solubility product expression for Ag2S is:
Ksp  Ag   S   10.  10
 2 2 49
146
 The dissolution of solid calcium phosphate in

water is represented as:
    
H 2O
3 2 3
2+
Ca 3 PO4  
3 Ca 2 PO4
2  s 100%
 The solubility product constant expression is:

You do it!
Ksp  Ca  2 3
 3 2
PO4  10  .  10 25
147
 In general, the dissolution of a slightly soluble

compound and its solubility product expression
are represented as:

M r Ys s 

H 2O
r M s
 s Y r
100%
Ksp  M   Y 
s r r s
148
 The same rules apply for compounds that have

more than two kinds of ions.
 One example of a compound that has more than
two kinds of ions is calcium ammonium
phosphate.
 2 1 3
CaNH4 PO 4s   Ca aq   NH4aq   PO 4aq 
  
K sp  Ca 2 NH4 PO34 
149
Determination of Solubility Product
Constants
 Example 20-1: One liter of saturated silver chloride
solution contains 0.00192 g of dissolved AgCl at
25oC. Calculate the molar solubility of, and Ksp for,
AgCl.
 The molar solubility can be easily calculated from
the data:
? mol AgCl 0.00192 g AgCl 1 mol AgCl
 
L L 143 g AgCl
5 mol AgCl
 1.34 10
L
150
Constants
 The equation for the dissociation of silver chloride,
the appropriate molar concentrations, and the
solubility product expression are:

AgCl s  Ag 
 Cl 
1.34  10 M 1.34  10 M
-5 -5

Ksp  Ag 
Cl 

151
Constants
 Substitution of the molar concentrations into the
solubility product expression gives:
Ksp  Ag Cl 

 
 134
.  10 134
.  10 
5 5
10
 18
.  10
152
Constants
 Example 20-2: One liter of saturated calcium
fluoride solution contains 0.0167 gram of CaF2 at
25oC. Calculate the molar solubility of, and Ksp
for, CaF2.
1. Calculate the molar solubility of CaF2.
? mol CaF2 0.0167 g CaF2 1 mol

 
L 1.0 L 78.1 g
 4 mol CaF2
 2.14 10
L
153
Constants
 From the molar solubility, we can find the ion
concentrations in saturated CaF2. Then use those
values to calculate the Ksp.
 Note: You are most likely to leave out the factor of 2 for the
concentration of the fluoride ion!
CaF 
CaF22 
 Ca2+2
Ca 
aq  2- F1-
+ 2F aq 
 4 4 4 4 4
.14
2.214 1010 MM2.214  10
.14 10M M 2(2(
2.214  10
.14 10M4 M
) )

K sp  Ca F 
2  2
 2.14  10 4.28  10 
4 4 2
 3.92  10 11
154
Uses of Solubility
Product Constants
 The solubility product constant can be used to
calculate the solubility of a compound at 25oC.
 Example 20-3: Calculate the molar solubility of
barium sulfate, BaSO4, in pure water and the
concentration of barium and sulfate ions in
saturated barium sulfate at 25oC. For barium
sulfate, Ksp= 1.1 x 10-10.
155
Uses of Solubility
Product Constants
 Make the algebraic substitution of x‟s into
solubility product expression and solve for x,
giving the ion concentrations.
x x   1.110 10
5
x  1.0 10 M
Ba   SO   1.0 10
2 2
4
5
M
156
Uses of Solubility
Product Constants
 Finally, to calculate the mass of BaSO4 in 1.00 L
of saturated solution, use the definition of
molarity.
5
? g BaSO 4 1.0 10 mol 234 g
 
L L mol
3 g BaSO 4
 2.3 10
L
157
Uses of Solubility
Product Constants
 Example 20-4: The solubility product constant
for magnesium hydroxide, Mg(OH)2, is 1.5 x
10-11. Calculate the molar solubility of
magnesium hydroxide and the pH of a
saturated magnesium hydroxide solution at
25oC.
You do it!
158
Uses of Solubility
Product Constants
 Be careful, do not forget the stoichiometric
coefficient of 2!
 2 
Mg(OH) 2  Mg aq   2 OH  aq 
xM  xM 2 xM
Ksp  Mg  2
OH  2
159
Uses of Solubility
Product Constants
 Substitute the algebraic expressions into the
solubility product expression.
 x 2 x   15
2
.  10 11
11
4 x  15
3
.  10
12
x  3.75  10
3
4
x  1.6  10  molar solubility
160
Uses of Solubility
Product Constants
 Solve for the pOH and pH.
 x 2 x   15
2
.  1011
.  1011
4 x 3  15
12
x  3.75  10
3
4
x  16
.  10  molar solubility
OH   2  M  3.2  10
- 4
M
pOH  3.49 pH  10.51
161
The Common Ion Effect in Solubility
Calculations
 Example 20-5: Calculate the molar
solubility of barium sulfate, BaSO4, in
0.010 M sodium sulfate, Na2SO4, solution
at 25oC. Compare this to the solubility of
BaSO4 in pure water. (Example 20-3).
(What is the common ion? How was a
common ion problem solved in Chapter
19?)
162
Calculations
1. Write equations to represent the equilibria.
2
Na 2SO 4 
 2 Na  SO
1 0 0% +
4
0.010 M 2(0.010 M ) (0.010 M )

BaSO 4s  
 Ba 2
 SO 2
aq  4 aq 
xM xM xM
163
Calculations
2. Substitute the algebraic representations of the
concentrations into the Ksp expression and
solve for x.
  
K sp  Ba 2 SO 24  1.110 10
  x 0.010  x 
The simplifyin g assumption can be applied.
0.010  x   0.010
0.010 x = 1.110-10
x  1.110 8  molar solubility of BaSO 4
164
Calculations
 The molar solubility of BaSO4 in 0.010 M Na2SO4
solution is 1.1 x 10-8 M.
 The molar solubility of BaSO4 in pure water is 1.0 x 10-
5 M.
 BaSO4 is 900 times more soluble in pure water than in

0.010 M sodium sulfate!
 Adding sodium sulfate to a solution is a fantastic method to
remove Ba2+ ions from solution!
 If your drinking water were suspected to have lead ions
in it, suggest a method to prove or disprove this
suspicion.
165
The Reaction Quotient in
Precipitation Reactions
 The reaction quotient, Q, and the Ksp of a
compound are used to calculate the
concentration of ions in a solution and
whether or not a precipitate will form.
 Example 20-6: We mix 100 mL of 0.010 M
potassium sulfate, K2SO4, and 100 mL of
0.10 M lead (II) nitrate, Pb(NO3)2 solutions.
Will a precipitate form?
166
1. Write out the solubility expressions.
H 2O 100% 2
K2SO4  
 2 K  +
SO4
Pb NO3 2   H 2 O 100%
 Pb 2+
2 -
NO3
Will PbSO4 precipitate?
167
 Calculate the Qsp for PbSO4.
 Assume that the solution volumes are additive.
 Concentrations of the important ions are:
100 mL 0.10

100 mL 0.10MM
M Pb2+2+  00.050
.050MMPb
Pb2+2+
200
200mL
mL
100 mL  0.010 M
MSO2-   0.0050 M SO4 2-
4
200 mL
168
 Finally, calculate Qsp for PbSO4 and compare it to
the Ksp.

Qsp  Pb 2
 2
SO4 
  0.050 0.0050
4
 2.5  10
8
Ksp  18
.  10 for PbSO 4
Qsp  Ksp therefore solid forms
169
 Example 20-7: Suppose we wish to remove
mercury from an aqueous solution that contains
a soluble mercury compound such as Hg(NO3)2.
We can do this by precipitating mercury (II) ions
as the insoluble compound HgS. What
concentration of sulfide ions, from a soluble
compound such as Na2S, is required to reduce
the Hg2+ concentration to 1.0 x 10-8 M? For
HgS, Ksp=3.0 x 10-53.
You do it!
170
 HgS
Hg 2  S2 
  
K sp  Hg 2 S2  3.0 10 53
solve for S 
2
S   Hg 
2
K sp
2

3.0 10 53
1.0 10 8
 3.0  10  45
M
If enough S2- , in the form of Na 2S, is added to just

slightly exceed 3.0 10  45 M the mercury wi ll precipitat e.
171
 Example 20-8: Refer to example 20-7. What
volume of the solution (1.0 x 10-8 M Hg2+ )
contains 1.0 g of mercury?
2
2 1 mol Hg 1.0 L
? L  1.0 g Hg  2

201 g Hg 1.0 10 8 mol Hg 2
 5.0 105 L  125,000 gal
172
 This chapter was long but essential to your

understanding of Chemistry!
 Make sure you understand this chapter‟s
concepts!
173
Unit Goals
1. Chemical Equilibrium Basic Concepts

2. The Equilibrium Constant and Reaction Quotient
3. Le Chatelier‟s Principle
4. Partial Pressures and Kc –Kp Relationship
5. Ionic Equilibria Basic Concepts
6. The pH and pOH scales
7. Ionization constants for Acids and Bases
8. Solubility Product Principle
174
CHM12-3
Lecture Unit 5
 BASIC CHEMICAL AND IONIC EQUILIBRIA
175
THERMOCHEMISTRY

School of Chemical Engineering and Chemistry
Mapua Institute of Technology
1
Outline
1. Principles of heat flow
2. Measurement of heat flow; calorimetry
3. Enthalpy
4. Thermochemical equations
5. Enthalpies of formation
6. Bond enthalpy
7. The first law of thermodynamics
Principles of Heat Flow
 Definitions
 The system: that part of the universe on which
attention is focused
 The surroundings: the rest of the universe
 Practically speaking, it is possible to consider only the
surroundings that directly contact the system
Figure 6.1 – Systems and Surroundings
Chemical Reactions
 When we study a chemical reaction, we
consider the system to be the reactants and
products
 The surroundings are the vessel (beaker, test
tube, flask) in which the reaction takes place
plus the air or other material in thermal
contact with the reaction system
Forms of Energy
 Two broad categories of energy: potential
energy and kinetic energy.
 Potential energy - associated with the relative

position of an object.
 Kinetic energy - associated with motion.

1 2
Kinetic energy = mv
2
Forms of Energy
 Internal energy - the combined kinetic and
potential energies of atoms and molecules that
make up an object or system.
 Chemical energy - energy released or

absorbed during a chemical reaction.
 Other forms of energy include radiant,

mechanical, thermal, electrical, and nuclear.
Heat and Work
 Heat is the flow of energy between two
objects because of a difference in
temperature.
 Heat flows from the warmer object to the cooler

object.
 Work is the transfer of energy accomplished
by a force moving a mass some distance
against resistance.
State Properties
 The state of a system is specified by
enumerating:
 Composition
 Temperature
 Pressure
 State properties depend only on the state of
the system, not on the path the system took to
reach the state
 Mathematically for a state property X:
 ΔX is the change in X
 ΔX = Xfinal – Xinitial
Direction and Sign of Heat Flow
 Heat is given the symbol, q
 q is positive when heat flows into the system
from the surroundings
 q is negative when heat flows from the system
into the surroundings
 Endothermic processes have positive q
 H2O (s)  H2O (ℓ) q>0
 Exothermic processes have negative q
 CH4 (g) + 2O2 (g)  CO2 (g) + H2O (ℓ) q < 0
Exothermic and Endothermic Processes
Magnitude of Heat Flow
 In any process, we are interested in both the
direction of heat flow and in its magnitude
 q is expressed in joules (or kilojoules)
 James Joule (1818-1889); calorimetry
 Alternate unit: calorie
 1 calorie = 4.184 J
 1 kilocalorie = 4.184 kJ
 Nutritional calories are kcal
The Calorimetry Equation
 q = C x Δt
 Δt = tfinal – tinitial
 C (uppercase) is the heat capacity of the system:
it is the quantity of heat needed to raise the
temperature of the system by 1 °C
 q = m x c x Δt
 c (lowercase) is the specific heat: the quantity of
heat needed to raise the temperature of one gram
of a substance by 1 °C
 c depends on the identity and phase of the
substance
Heat Capacity and Specific Heat
 The amount of heat energy absorbed can be quantified.
q  mcT
q  nC p T
Heat Capacity and Specific Heat
 Specific heat and molar heat capacities for some

common substances.
Example Problem 2
 Heating a 24.0 g aluminum can raises its
temperature by 15.0ºC. Find the value of q for
the can.
Example Problem 3
 The molar heat capacity of liquid water is 75.3
J/mol K. If 37.5 g of water is cooled from 42.0
to 7.0ºC, what is q for the water?
Specific Heat
 The specific heat of a substance, like the
density or melting point, is an intensive
property that can be used to identify a
substance or determine its purity
 Water
 Water has an unusually large specific heat
 A large quantity of heat is required to raise the
temperature of water
 Climate is moderated by the specific heat of water
 Only two states in the US have never recorded
temperatures over 100 °F – one is Alaska (cold North)
and the other is Hawaii (moderated by water)
Table 6.1
Example 6.1
Measurement of Heat Flow:
Calorimetry
 A calorimeter is a device used to measure the
heat flow of a reaction
 The walls of the calorimeter are insulated to
block heat flow between the reaction and the
surroundings
 The heat flow for the system is equal in
magnitude and opposite in sign from the heat
flow of the calorimeter
 qreaction = - qcalorimeter
 qreaction = - Ccal Δt
Calorimetry
 Heat flow is measured using a calorimeter.
 A calorimeter measures the heat evolved or

absorbed by the system of interest by
measuring the temperature change in the
surroundings.
qsystem =  qsurroundings
qgained =  qlost
Example Problem 9.4
 A glass contains 250.0 g of warm water at
78.0ºC. A piece of gold at 2.30ºC is placed in
the water. The final temperature reached by
this system is 76.9ºC. What was the mass of
gold? The specific heat of water is 4.184
J/gºC, and that of gold is 0.129 J/gºC.
Calorimetry
 There are two steps in a calorimetric
measurement.
 Calibration - the calorimeter constant, Ccalorimeter,

is determined by dividing the known amount of
heat released in the calorimeter by the
temperature change of the calorimeter.
q = Ccalorimeter  T
 Actual Measurement - heat released or absorbed
in a reaction of known quantity of material is
measured.
Calorimetry
 Actual Measurement - temperature change for
the calorimeter and the calorimeter constant
are used to determine the amount of heat
released by a reaction.
qcalorimeter = Ccalorimeter  Tcalorimeter

qreaction =  qcalorimeter
Calorimetry
 Diagram of a bomb calorimeter and standard

choice for system and surroundings in a bomb
calorimetry experiment.
Example Problem 9.5
 In the calibration of a calorimeter, an
electrical resistance heater supplies 100.0 J of
heat and a temperature increase of 0.850ºC is
observed. Then, 0.245 g of a particular fuel is
burned in this same calorimeter and the
temperature increases by 5.23ºC. Calculate the
energy density of this fuel, which is the
amount of energy liberated per gram of fuel
burned.
Figure 8.2
Coffee-cup Calorimeter
 For a reaction performed in a coffee-cup calorimeter
J
qreac tion  mwater  4.18   t
g C
Example 6.2
Figure 6.3
Bomb Calorimeter
 The bomb calorimeter is more versatile than
the coffee-cup calorimeter
 Reactions involving high temperature
 Reactions involving gases
 The bomb is a heavy metal vessel that is
usually surrounded by water
 qreaction = -qcalorimeter
 qreaction = -CcalΔt
 Ccal is a function of the calorimeter and can be
measured experimentally
Example 8.3
Enthalpy
 The heat flow at constant pressure is equal to
the difference in enthalpy (heat content)
between products and reactants
 The symbol for enthalpy is H
 We measure changes in enthalpy using a
calorimeter and a reaction run at constant
pressure:
 ΔH = Hproducts – Hreactants
 The sign of the enthalpy change is the same as
for heat flow:
 ΔH > 0 for endothermic reactions
 ΔH < 0 for exothermic reactions
 Enthalpy is a state variable
Enthalpy
 The conditions under which heat flow, q,
occurs will have an impact on the
measurement that is made.
 Combustion of octane releases 5.45 x 103 kJ

under constant volume conditions, represented as
qv.
 Combustion of octane releases 5.48 x 103 kJ
under constant pressure conditions, represented as
qp.
Defining Enthalpy
 The internal energy change for a reaction
equals the sum of the heat flow and the work.
E  q  w
 During an expansion, w = –PV.
E  q  PV
 Under constant volume conditions, V = 0, and

E = qv. E  q v
Defining Enthalpy
 Enthalpy is the heat flow under conditions of
constant pressure.
 The enthalpy change can be expressed as
H  E  PV H  E  (PV )
H  (q  PV )  (PV )
H  q  PV  PV
H  qp
Defining Enthalpy
 When a system releases heat, the process is
said to be exothermic.
 The value of H is less than zero; the sign on H
is negative
 When a system absorbs heat, the process is
said to be endothermic.
 The value of H is greater than zero; the sign on
H is positive.
H of Phase Changes
 Phase changes occur under constant pressure
conditions.
 The heat flow during a phase change is an enthalpy change.
 During a phase change, temperature does not change with heat flow
due to formation or breaking of intermolecular attractive forces.
∆H of Phase Changes
 The heat required to convert a liquid to a gas is the
heat of vaporization, Hvap.
 Hvap is endothermic with a positive value.
 The heat released to convert a gas to a liquid is the
heat of condensation, Hcond.
 Hcond is exothermic with a negative value.
 Hcond = –Hvap
 The values of enthalpy changes in opposite directions
have equal numeric values and differ only in their
signs.
 The magnitude of enthalpy change depends on the
substance involved.
 Standard molar enthalpies and temperatures for

phase changes of water.
 The value of H for a phase change is
compound specific and has units of kJ/mol.
 The heat flow can be calculated using the number

of moles of substance, n, and the value of the
enthalpy change.
H  n  Hphase change
 Heat curve for the heating of 500-g of ice at -50oC

to 200oC.
Example Problem
 Calculate the enthalpy change when 240. g of
ice melts.
Bonds and Energy
 The enthalpy change for a reaction can be estimated
using bond energies.
 During a chemical reaction, reactant bonds are
broken and product bonds are made.
 Breaking bonds requires energy.
 Making bonds releases energy.
 If the amount of energy released making product
bonds is greater than the amount of energy required
to break reactant bonds, the reaction is exothermic. If
the energy released is less than the energy required,
the reaction is endothermic.
Bonds and Energy
CH 4  2O2  CO2  2H 2O
 The combustion of methane breaks 4 C-H bonds

and 2 O=O bonds. 2 C=O bonds and 4 O-H bonds
are made.
Bonds and Energy
 The accuracy of enthalpy changes calculated from
tabulated bond energies is not very good.
 The bond energies used are averages.
 Bond energy method used to estimate enthalpy changes
for reactions involving compounds with no available
thermochemical data.
 A thermochemical equation summarizes the overall
energetics for a chemical reaction.
 The sign on the H indicates whether the reaction is
endothermic or exothermic
CH 4 (g) + 2O2 (g) 
 CO2 (g) + 2H 2O(l )
H  890.4 kJ
Bonds and Energy
 The combustion of methane is an exothermic reaction and
releases 890.4 kJ of heat energy when 1 mole of methane
reacts with 2 moles of oxygen.
CH 4 (g) + 2O2 (g) 
 CO2 (g) + 2H 2O(l )
H  890.4 kJ
2CH 4 (g) + 4O2 (g) 
 2CO2 (g) + 4H2O(l )
H  1780.8 kJ
 For thermochemical equations, if the stoichiometric
coefficients are multiplied by some factor, the heat of reaction
must also be multiplied by the same factor.
Heats of Reaction for Some Specific Reactions
 Some classes of chemical reactions are given

their own labels for heats of reactions.
 Heat of combustion, Hcomb
 Heat of neutralization, Hneut
 Heat of formation, Hf, is the heat of reaction for
formation of substances.
1
C(s) + O 2 (g) 
 CO(g)
2
Fractional coefficients are allowed for formation reactions
because only one mole of product can be formed.
Heats of Reaction for Some Specific Reactions
 A formation reaction is the chemical reaction
by which one mole of a compound is formed
from its elements in their standard states.
 The standard state is the most stable form of

an element at room temperature, 25oC, and
pressure, 1 atm, indicated with a superscript o.
 Hfo = 0 for an element in its standard state.

Hess’s Law and Heats of Reaction
 Direct calorimetric determinations of some reactions
may be too difficult or dangerous to perform.
 An indirect method is needed to obtain heats of reaction.
 Hess’s law: the enthalpy change for any process is
independent of the particular way the process is
carried out.
 Enthalpy is a state function.
 A state function is a variable whose value depends only
on the state of the system and not its history.
Hess’s Law
 Conceptual diagram representing Hess’s law.

Enthalpy is a state function, so any convenient
path can be used to calculate the enthalpy change.
Hess’s Law
 Enthalpy diagram for the combustion of methane. The

CH4 is converted to CO, then the CO is converted to CO2.
The H for each step is used to calculate the H for the
overall reaction. The H will be the same for both paths.
Example Problem
 One origin of SO3 is the combustion of sulfur,
which is present in small quantities in coal,
according to the following equation.
3
S(s)  O2 (g)  SO3 (g)
2
S(s)  O2 (g)  SO2 (g) H o  296.8 kJ
2SO2 (g)  O2 (g)  2SO3 (g) H o  197.0 kJ
 Given the thermochemical information below,
determine the heat of reaction for this
reaction.
Formation Reactions and Hess’s Law
 Conceptual diagram showing how to use tabulated

enthalpies of formation to calculate the enthalpy
change for a chemical reaction.
Formation Reactions and Hess’s Law
 The enthalpy change for a reaction can be
calculated using Hess’s law and heats of
formation.
H = vi H (products)i   v j H (reactants) j
o o
f
o
f
i j
Example Problem 9.8
 Use tabulated data to find the heat of
combustion of one mole of propane, C3H8, to
form gaseous carbon dioxide and liquid water.
Example Problem 9.9
 Ethanol, C2H5OH, is used to introduce oxygen
into some blends of gasoline. It has a heat of
combustion of 1366.8 kJ/mol. What is the
heat of formation of ethanol?
Energy and Stoichiometry
 A thermochemical equation allows for the
stoichiometric treatment of energy.
 For an exothermic reaction, energy is treated as a product.
 For an endothermic reaction, energy is treated as a
reactant.
 The thermochemical equation is used to convert
between the number of moles of a reactant or
product and the amount of energy released or
absorbed.
 The stated value of H for a thermochemical equation
corresponds to the reaction taken place exactly as written,
with the indicated numbers of moles of each substance
reacting.
Energy and Stoichiometry
 Flow chart detailing the sequence of steps needed to

calculate the amount of energy released or absorbed
when a chemical reaction is carried out using a given
amount of material.
Thermochemical Equations
 A thermochemical equation is a chemical equation with the ΔH
for the reaction included
 Example
 NH4NO3 (s)  NH4+ (aq) + NO3- (aq)
 Experiment gives qreaction = 351 J for one gram of ammonium
nitrate
 For one mole, this is
351J 80 .05 g
  2.81 X 10 4 J  28 .1kJ
1.00 g 1mol
 The thermochemical equation is

 NH4NO3 (s)  NH4+ (aq) + NO3- (aq) ΔH = +28.1 kJ
Conventions for Thermochemical
Equations
1. The sign of ΔH indicates whether the reaction
is endothermic or exothermic
2. The coefficients of the thermochemical
equation represent the number of moles of
reactant and product
3. The phases of all reactant and product species
must be stated
4. The value of ΔH applies when products and
reactants are at the same temperature, usually 25
°C
Rules of Thermochemistry
1. The magnitude of ΔH is directly proportional
to the amount of reactant or product
2. ΔH for the reaction is equal in magnitude but
opposite in sign for ΔH for the reverse of the
reaction
3. The value of ΔH is the same whether the
reaction occurs in one step or as a series of
steps
This rule is a direct consequence of the fact that ΔH
is a state variable
This rule is a statement of Hess’s Law
Example 6.4
Enthalpy of Phase Changes
 Phase changes involve enthalpy
 There is no change in temperature during a phase change
 Endothermic: melting or vaporization
 Exothermic: freezing or condensation
 Pure substances have a value of ΔH that corresponds to melting
(reverse, fusion) or vaporization (reverse, condensation)
Example 6.5
Example 6.6
Recap of the Rules of Thermochemistry
 ΔH is directly proportional to the amount of
reactant or product
 If a reaction is divided by 2, so is ΔH
 If a reaction is multiplied by 6, so is ΔH
 ΔH changes sign when the reaction is
reversed
 ΔH has the same value regardless of the
number of steps
Enthalpies of Formation Hf
 The standard molar enthalpy of formation, , is equal to the

enthalpy change
 For one mole of a compound
 At constant pressure of 1 atm
 At a fixed temperature of 25 °C
 From elements in their stable states at that temperature and
pressure
 Enthalpies of formation are tabulated in Table 8.3 and in Appendix
1 in the back of the textbook
Table 6.3
Table 6.3, (Cont’d)
Table 6.3, (Cont’d)
Enthalpies of Formation of Elements and of H+ (aq)
 The enthalpy of formation of an element in its standard state at 25

°C is zero
HfBr2 (l )  HfH2O(l )  0
 The enthalpy of formation of H+ (aq) is also zero

Calculation of ΔH°
H   Hf products   Hf reactants
 The symbol Σ refers to “the sum of”

 Elements in their standard states may be
omitted, as their enthalpies of formation are
zero
 The coefficients of reactants and products in
the balanced equation must be accounted for
Example 6.7
Example 6.8
The First Law of Thermodynamics
 Thermodynamics
 Deals with all kinds of energy effects in all kinds
of processes
 Two types of energy
 Heat (q)
 Work (w)
 The Law of Conservation of Energy
 ΔEsystem = - ΔEsurroundings
 The First Law
 ΔE = q + w
 The total change in energy is equal to the sum of the
heat and work transferred between the system and
the surroundings
Conventions
 q and w are positive
 When the heat or work enters the system from the
surroundings
 q and w are negative
 When the heat or work leaves the system for the
surroundings
Energy Transformation and Conservation of Energy
 For a system or surroundings, the only

possible forms of energy flow are heat, q, and
work, w.
E = q  w
 The delta, , means “change in” and is
defined as the difference in the final and
initial states.
E = Efinal  Einitial
Example Problem
 If 515 J of heat is added to a gas that does 218
J of work as a result, what is the change in the
energy of the system?
 The sign resulting from the difference in the

final and initial states indicates the direction
of the energy flow.
 Negative values indicate energy is being released.
 Positive values indicate energy is being absorbed.

 First law of thermodynamics states that

energy can be transformed from one form to
another but cannot be created or destroyed.
Euniverse = Esurroundings + Esystem  0

Figure 8.10
Example 6.9
Heat
 Ordinarily, when a chemical reaction is
carried out in the laboratory, energy is
evolved as heat
 CH4 (g) + 2O2 (g)  CO2 (g) + H2O (ℓ) ΔE = -
885 kJ
 The combustion of methane in a Bunsen burner
produces nearly 885 kJ of heat per mol
 The decrease in volume that takes place is a 1%
work effect
Work
 In an internal combustion engine, a significant
fraction of the energy of combustion is
converted to useful work
 The expansion of the combustion gases produces
a volume and a pressure change
 The system does work on its surroundings
 Propels the car forward
 Overcomes friction
 Charges battery
 Like ΔH, ΔE is a state variable
 q and w are not state variables
Figure 6.11 – Pressure-Volume Work
ΔH and ΔE
 Constant pressure
 Coffee-cup calorimeter
 ΔH = qp
 Constant volume
 In a bomb calorimeter, there is no pressure-
volume work done
 ΔE = qv
ΔH and ΔE, (Cont’d)
 H = E + PV
 ΔH = ΔE + PΔV
 The PV product is important only where gases are
involved; it is negligible when only liquids or
solids are involved
 ΔH = ΔE + ΔngRT
 Δng is the change in the number of moles of gas
as the reaction proceeds
Example 8.10
End of Chapter 15
 Fireworks are beautiful exothermic
chemical reactions.
96
THERMOCHEMISTRY

97
General Chemistry 1
Lecture Unit No. 4
(Stoichiometry)

1
Outline
1. Atomic, Molar/Molecular Mass

2. The Mole Concept
3. Percentage Composition by Mass
4. Empirical Formula
5. Molecular Formula
Stoichiometry
• Chemical arithmetic
• Study of mass relationships in chemistry
• quantitative
Atomic Mass
-interchangeably used with
Atomic Weight
•Weighted average of the

masses of the constituent
isotopes of an element.
 Tells us the atomic masses
of every known element.
 Lower number on periodic
chart.
•How do we know what the
values of these numbers
are?
4
Molar Mass
• How do we calculate the molar mass of a compound?
 add atomic weights of each atom
• The molar mass of propane, C3H8, is:
3 C 3 12.01 amu 36.03 amu

8 H 8 1.01 amu 8.08 amu
Molar mass 44.11 amu
5
Molar Mass
The molar mass of calcium nitrate, Ca(NO3)2 , is:
You do it!
6
Molar Mass
1 Ca 1 40.08 amu 40.08 amu

2 N 2 14.01 amu 28.02 amu
6 O 6 16.00 amu 96.00 amu
Molar mass 164.10 amu
7
Molar Mass of Ionic Compounds
Ionic compounds do not contain molecules.
Don’t use “molecular weight” to describe
mass.
Formula weight is the correct name
• Molar mass can be used
atomic wts Formula wt. Molar
mass
Compound amu amu g/mol
NaCl 22.99 + 35.45 58.44
Ca(NO3)2 40.08+2(14.01)+6(16.00) 164.10
The Mole Concept
• A number of atoms, ions, or molecules that is

large enough to see and handle.
• A mole = number of things
 Just like a dozen = 12 things
 One mole = 6.022 x 1023 things
• Avogadro’s number = 6.022 x 1023
 Symbol for Avogadro’s number is NA.
9
Avogadro’s Number
• There is a number that corresponds to a collection of
atoms where the mass of that collection in grams is
numerically equal to the same number in amu, for a
single atom
• NA = 6.022 X 1023
• Number of atoms of an element in a sample whose
mass is numerically equal to the mass of a single
atom
• By knowing Avogadro’s number and the atomic
mass, it is now possible to calculate the mass of a
single atom in grams
Figure 4.1 – One Mole of Several Substances
The Mole Concept
•How do we know when we have a mole?
 count it out
 weigh it out
•Molar mass - mass in grams numerically
equal to the atomic weight of the element in
grams.
•H has an atomic weight of 1.00794 g
 1.00794 g of H atoms = 6.022 x 1023 H atoms
•Mg has an atomic weight of 24.3050 g
 24.3050 g of Mg atoms = 6.022 x 1023 Mg atoms
12
The Mole Concept
A mole of XmYn contains:
m moles of atom X and n moles of atom Y
1 mol of H2O contains:
2 mol of H atoms and 1 mol of O atoms
Molar mass = sum of the atomic masses
Mass of 1 water molecule:

= 2(1.008 amu) + 1(15.999 amu) =
18.015 amu
Molar mass of water:
= 2(1.008 g/mol) + 1(15.999 g/mol) =
18.015 g/mol
The Mole Concept
• Example 4-1. How many atoms are contained in 1.67
moles of Mg?
? Mg atoms
14
The Mole Concept
moles of Mg?
? Mg atoms 1.67 mol Mg
15
The Mole Concept
moles of Mg?
6.022 10 23 Mg atoms
1 mol Mg
16
The Mole Concept
moles of Mg?
6.022 10 23 Mg atoms
1 mol Mg
1.00 10 24 Mg atoms
17
The Mole Concept
moles of Mg?
6.022 1023 Mg atoms

1 mol Mg
1.00 1024 Mg atoms
18
The Mole
Example 4-2: How many moles of Mg

atoms are present in 73.4 g of Mg?
You do it!
19
The Mole Concept
•Example 4-2: How many moles of Mg

? mol Mg 73.4 g Mg
20
The Mole Concept

1 mol Mg atoms
? mol Mg 73.4 g Mg
24.30 g Mg
21
The Mole Concept

1 mol Mg atoms
? mol Mg 73.4 g Mg
24.30 g Mg
3.02 mol Mg
22
Mole-Gram Conversions
• m = MM X n
 m = mass
 MM = molar mass
 n = number of moles
Formula Weights, Molecular Weights, and
Moles
One Mole of Contains

Cl2 or 70.90g 6.022 x 1023 Cl2 molecules
2(6.022 x 1023 ) Cl atoms
C3H8 You do it!
24
The Mole Concept
•One Mole of Contains

 Cl2 or 70.90g 6.022 x 1023 Cl2 molecules
2(6.022 x 1023 ) Cl atoms
 C3H8 or 44.11 g 6.022 x 1023 C3H8 molecules
3 (6.022 x 1023 ) C atoms
8 (6.022 x 1023 ) H atoms
25
The Mole Concept
• Example 4-3: Calculate the number of C3H8
molecules in 74.6 g of propane.
? C3H8 molecules 74.6 g C3H8
26
The Mole Concept
• Example 4-3 : Calculate the number of C3H8
? C3 H 8 molecules 74.6 g C3 H 8
1 mole C3 H 8
44.11 g C3 H 8
27
The Mole Concept
? C3H8 molecules 74.6 g C3H8

23
1 mole C3H8 6.022 10 C3H8 molecules
44.11 g C3H8 44.11 g C3H8
28
The Mole Concept
? C3H 8 molecules 74.6 g C3H 8

23
1 mole C3 H 8 6.022 10 C3H 8 molecules
44.11 g C3 H 8 44.11 g C3H 8
24
1.02 10 molecules
29
The Mole Concept
Example 4-4. Calculate the number of O atoms

in 26.5 g of Li2CO3.
You do it!
30
The Mole Concept
• Example 4-4. Calculate the number of O atoms

in 26.5 g of Li2CO3.
1 mol Li 2 CO3
? O atoms 26.5 g Li 2 CO3
73.8 g Li 2 CO3
6.022 10 23 form. units Li 2 CO3 3 O atoms
1 mol Li 2 CO3 1 formula unit Li 2 CO3
6.49 10 23 O atoms
31
The Mole Concept
• Occasionally, we will use millimoles.
 Symbol - mmol
 1000 mmol = 1 mol
• For example: oxalic acid (COOH)2
 1 mol = 90.04 g
 1 mmol = 0.09004 g or 90.04 mg
32
The Mole Concept
Example 4-5: Calculate the number of mmol in 0.234
g of oxalic acid, (COOH)2.
You do it!
33
The Mole Concept
• Example 4-5: Calculate the number of mmol in 0.234
g of oxalic acid, (COOH)2.
? mmol (COOH)2 0.234 g (COOH)2

1 mmol (COOH)2
2.60 mmol (COOH)2
0.09004 g (COOH)2
34
Percent Composition
• % composition = mass of an individual element in a

compound divided by the total mass of the compound x
100%
• Determine the percent composition of C in C3H8.
mass C
%C 100%
mass C3 H 8
3 12.01 g
100%
44.11 g
81.68% 35
Percent Composition
What is the percent composition of H in

C3H8?
You do it!
36
Percent Composition
•What is the percent composition of H in

C3H8?
mass H
%H 100%
mass C3 H 8
8 H
100%
C3 H 8
8 1.01 g
100% 18.32%
44.11 g
or
18.32% 100% 81.68%
37
Percent Composition
• Example 4-6: Calculate the percent composition of
Fe2(SO4)3 to 3 significant figures.
You do it!
38
Percent Composition
• Example 4-6: Calculate the percent composition of
Fe2(SO4)3 to 3 sig. fig.
2 Fe 2 55.8 g
% Fe 100% 100% 27.9% Fe
Fe 2 (SO 4 ) 3 399.9 g
3 S 3 32.1 g
%S 100% 100% 24.1% S
Fe 2 (SO 4 ) 3 399.9 g
12 O 12 16.0 g
% O 100% 100% 48.0% O
Fe 2 (SO 4 ) 3 399.9 g
Total 100%
39
Empirical Vs. Molecular Formula
• Empirical Formula - smallest whole-number ratio

of atoms present in a compound
 CH2 is the empirical formula for alkenes
 No alkene exists that has 1 C and 2 H’s
• Molecular Formula - actual numbers of atoms of
each element present in a molecule of the
compound
 Ethene – C2H4
 Pentene – C5H10
• We determine the empirical and molecular
formulas of a compound from the percent
composition of the compound.
 percent composition is determined experimentally
40
•Example 4-7: A compound contains 24.74%
K, 34.76% Mn, and 40.50% O by mass.
What is its empirical formula?
•Make the simplifying assumption that we
have 100.0 g of compound.
•In 100.0 g of compound there are:
 24.74 g of K
 34.76 g of Mn
 40.50 g of O
41
1 mol K
? mol K 24.74 g K 0.6327 mol K
39.10 g K
42
1 mol K
? mol K 24.74 g K 0.6327 mol K
39.10 g K
1 mol Mn
? mol Mn 34.76 g Mn 0.6327 mol Mn
54.94 g Mn
43
1 mol K
? mol K 24.74 g K 0.6327 mol K
39.10 g K
1 mol Mn
? mol Mn 34.76 g Mn 0.6327 mol Mn
54.94 g Mn
1mol O
? mol O 40.50 g O 2.531 mol O
16.00 g O
obtain smallest whole number ratio
44
1 mol K
? mol K 24.74 g K 0.6327 mol K
39.10 g K
1 mol Mn
? mol Mn 34.76 g Mn 0.6327 mol Mn
54.94 g Mn
1mol O
? mol O 40.50 g O 2.531 mol O
16.00 g O
0.6327 0.6327
for K 1K for Mn 1 Mn
0.6327 0.6327
45
1 mol K
? mol K 24.74 g K 0.6327 mol K
39.10 g K
1 mol Mn
? mol Mn 34.76 g Mn 0.6327 mol Mn
54.94 g Mn
1mol O
? mol O 40.50 g O 2.531 mol O
16.00 g O
0.6327 0.6327
for K 1K for Mn 1 Mn
0.6327 0.6327
2.531
for O 4O
0.6327
thus the chemical formula is KMnO 4
46
Example 4-8: A sample of a compound contains
6.541g of Co and 2.368g of O. What is empirical
formula for this compound?
You do it!
47
• Example 4-8: A sample of a compound

contains 6.541g of Co and 2.368g of O. What
is empirical formula for this compound?
1 mol Co
? mol Co 6.541 g Co 0.1110 mol Co
58.93 gCo
1mol O
? mol O 2.368 g O 0.1480 mol O
16.00 g O
find smallest whole number ratio
48
• Example 4-8: A sample of a compound

contains 6.541g of Co and 2.368g of O. What
is empirical formula for this compound?
0.1110 0.1480
for Co 1 Co for O 1.333O
0.1110 0.1110
multipy both by 3 to turn fraction to whole number
1 Co 3 3 Co 1.333 O 3 4O
Thus the compound' s formula is :
Co3O 4
49
Determination of Molecular Formulas
•Example 4-8: A compound is found to

contain 85.63% C and 14.37% H by
mass. In another experiment its molar
mass is found to be 56.1 g/mol. What is
its molecular formula?
 short cut method
1 mol contains 56.1 g
85.63% is C and 14.37% is H
56.1 g 0.8563 48.0 g of C
56.1 g 0.1437 8.10 g of H 50
Determination of Molecular Formulas
convert masses to moles

1 mol C
48.0 g of C 4 mol C
12.0 g C
1 mol H
8.10 g of H 8 mol H
1.01 g H
Thus the formula is :
C4 H8 51
Some Other Interpretations of Chemical Formulas
• Example 4-9: What mass of ammonium

phosphate, (NH4)3PO4, would contain 15.0 g of
N?
molar mass of (NH 4 )3 PO 4 149.0 g/mol

1 mol N
? mol N 15.0 g of N 1.07 mol N
14.0 g N
52

N?
molar mass of (NH 4 ) 3 PO 4 149.0 g/mol

1 mol N
14.0 g N
1 mol (NH 4 ) 3 PO 4
1.07 mol N 0.357 mol (NH 4 ) 3 PO 4
3 mol N
53

N?
molar mass of (NH 4 )3 PO 4 149.0 g/mol

1 mol N
14.0 g N
1 mol (NH 4 )3 PO 4
1.07 mol N 0.357 mol (NH 4 )3 PO 4
3 mol N
149.0 g (NH 4 )3 PO 4
0.357 mol (NH 4 )3 PO 4 53.2 g (NH 4 )3 PO 4
1 mol (NH 4 )3 PO 4
54
End of Lecture Unit No. 4 - Part I
• The mole concept and basic stoichiometry ideas
introduced in this chapter are essential components
for the remainder of this course.
55
Outline
1. Atomic, Molar/Molecular Mass

2. The Mole Concept
3. Percentage Composition by Mass
4. Empirical Formula
5. Molecular Formula
General Chemistry 1
Lecture Unit No. 4
(Stoichiometry)

57
PART II: Stoichiometry
© 2008 Brooks/Cole 1
Chemical Equations
Balanced equations obey the law of conservation of
mass (Lavoisier 1789).
“Mass is neither created nor destroyed in a chemical reaction.”
2 C2H6(g) + 7 O2(g) 4 CO2(g) + 6 H2O(l)

Nanoscale 2 molecules 7 molecules 4 molecules 6 molecules
Macroscale 2 moles 7 moles 4 moles 6 moles
2(30.0)= 60.0 g 7(32.0)= 224.0 g 4(44.0)= 176.0 g 6(18.0)= 108.0 g

284.0 g 284.0 g
C2H6 molar mass O2 molar mass
Chemical Equations
Stoichiometry
The relationship between the number of reactant and
product molecules in a chemical equation.
CaCO3(s) + 2 HNO3(aq)
Ca(NO3)2(aq) + CO2(g) + H2O(l)

A stoichiometric
coefficient
Fundamentals of Stoichiometry
• Stoichiometry is a term used to describe
quantitative relationships in chemistry.
 “How much?” of a product is produced or reactant is

consumed.
 Balanced chemical equation needed.
 Conversion between mass or volume to number of

moles frequently needed.
Ratios from a Balanced Chemical Equation
• Mole ratios are obtained from the coefficients in the balanced chemical
reaction.
 1 mol CH4 : 2 mol O2 : 1 mol CO2 : 2 mol H2O
• These ratios can be used in solving problems:

1 mol CH 4 2 mol H2O
or
2 mol O2 1 mol CH 4
Example Problem 4.1
• In the combustion of methane, how many moles of
O2 are required if 6.75 mol of CH4 is to be
completely consumed?
• This flow diagram illustrates the various steps

involved in solving a typical reaction stoichiometry
problem.
 No different than unit conversion
 Usually more than one conversion is necessary
 Write all quantities with their complete units
Example Problem 4.2
• How many grams of water can be produced if
sufficient hydrogen reacts with 26.0 g of oxygen?
• Solution to Problem 4.2 using the stoichiometry

problem flow diagram, Figure 4.3.
Example Problem 4.3
• If we have 153 g of S8 and an excess of
phosphorus, what mass of P4S3 can be produced
in the reaction shown?
8P4  3S8  8P4 S3
Limiting Reactants
• In many chemical reactions, one reactant is often
exhausted before the other reactants. This
reactant is the limiting reactant.
 Limiting reactant is determined using stoichiometry.
 The limiting reactant limits the quantity of product

produced.
Limiting Reactants
• Reaction between 6 H2
2H2 (g) + O2 (g) 
 2H2O(g) and 6 O2 will produce 6
H2O.
 6 H2 can produce 6 H2O.
 6 O2 can produce 12 H2O.
 H2 is limiting reactant.
 3 O2 left over.
Limiting Reactants
• In many cases, we manipulate the amounts of
reactants to ensure that one specific compound is
the limiting reactant.
 For example, a more expensive or scarce reagent is

usually chosen to be the limiting reagent.
• Other times, it is best to have a stoichiometric

mixture (equal ratio of moles) to prevent waste.
 For example, rocket fuel is designed so that no mass is

left over, which would add unnecessary weight to the
rocket.
Example Problem 4.4
• A solution of hydrochloric acid contains 5.22 g of
HCl. When it is allowed to react with 3.25 g of solid
K2CO3, the products are KCl, CO2, and H2O. Which
reactant is in excess?
Example Problem 4.5
• If 28.2 g of P4 is allowed to react with 18.3 g of S8,
which is the limiting reactant?
8P4  3S8  8P4 S3
Theoretical Yield
• The maximum mass of a product that can be
obtained in a reaction is determined by the limiting
reactant.
 Determine which reactant is the limiting reactant.
 Calculate the mass of product that can be made from the

limiting reactant. This mass is the theoretical yield.
 In stoichiometric mixtures, however, both reactants are

consumed completely, so either could be considered the
limiting reactant.
Theoretical and Percent Yields
• Many factors determine the amount of desired
product actually produced in a reaction.
 Temperature of the reaction
 The possibility of side reactions
 Further reaction of the product
 Time
Theoretical and Percentage Yields
 actual yield 
Percentage Yield =    100%
 theoretical yield 
• Reaction efficiency is measured with

percentage yield.
 The mass of product obtained is the actual yield.
 The ideal mass of product obtained

from calculation is the theoretical yield.
Example Problem 4.8
• In a laboratory experiment, a student heats 42.0 g
of NaHCO3 and determines that 22.3 g of Na2CO3
is formed. What is the percentage yield of this
reaction?
2NaHCO3 (s) Na2CO3 (s)  CO2 (g)  H2O(g)
heat
The Mole and Chemical Reactions
2 C2H6 (g) + 7 O2 (g) 4 CO2(g) + 6 H2O (l)
2 moles of C2H6 react with 7 moles of O2

2 moles of C2H6 produce 4 moles of CO2
2 mol C2H6 ≡ 7 mol O2
2 mol C2H6 ≡ 4 mol CO2 etc.
Mole ratios:
2 mol C2H6 7 mol O2
=1 2 mol C2H6 =1
7 mol O2
What mass of O2 and Br2 is produced by the reaction
of 25.0 g of TiO2 with excess BrF3?
3 TiO2(s) + 4 BrF3(l) 3 TiF4(s) + 2 Br2(l) + 3 O2(g)
Notes:
• Check the equation is balanced!
• Stoichiometric ratios:
3TiO2 ≡ 3O2 ; 3TiO2 ≡ 2Br2 ; and many others
• Excess BrF3 = enough BrF3 to react all the TiO2.
What mass of O2 and Br2 is produced by the reaction of 25.0g of TiO2 with
excess BrF3? 3 TiO2(s) + 4 BrF3(l) 3 TiF4(s) + 2 Br2(l) + 3 O2 (g)
nTiO2 = mass TiO2 / FM TiO2

1 mol
= 25.0 g x 79.88 g = 0.3130 mol TiO2
3 mol TiO2 ≡ 3 mol O2

3 mol O2
0.3130 mol TiO2 = 0.3130 mol O2
3 mol TiO2
What mass of O2 and Br2 is produced by the reaction of 25.0g of TiO2 with
excess BrF3? 3 TiO2(s) + 4 BrF3(l) 3 TiF4(s) + 2 Br2(l) + 3 O2(g)
Mass of O2 produced = nO2 (mol. wt. O2)

= 0.3130 mol x 32.00 g/mol
= 10.0 g
3 TiO2 ≡ 2 Br2
2Br2
nBr2 = 0.3130 mol TiO2 = 0.2087 mol Br2
3 TiO2
Mass of Br2 = 0.2087 mol 159.81 g = 33.4 g Br2

mol Br2
Practice Problem 4.8
The purity of Mg can be found by reaction with excess HCl
(aq), evaporating the water from the resulting solution and
weighing the solid MgCl2 formed.
Mg(s) + 2 HCl(aq) MgCl2(aq) + H2(g)
Calculate the % Mg in a 1.72-g sample that produced 6.46 g of
MgCl2 when reacted with excess HCl.
More difficult – What should you calculate?
– How much pure Mg will make 6.46 g of MgCl2?
– Express as a % of the original mass.
Mg + 2 HCl MgCl2 + H2
FW of MgCl2 = 24.31 + 2(35.45) = 95.21 g/mol
nMgCl2 = 6.46 g MgCl2 1 mol = 0.06785 mol MgCl2

95.21 g
Use mole ratio 1 mol Mg ≡ 1 mol MgCl2

1 Mg
Mg required: 0.06785 mol MgCl2
1 MgCl2
= 0.06785 mol of pure Mg
Mg + 2 HCl MgCl2 + H2
Calculate mass of pure Mg needed

0.06785 mol Mg x 24.31 g = 1.649 g Mg
1 mol
Given 1.72 g of impure Mg.
Purity (as mass %) = 1.649 g x 100% = 95.9 %

1.72 g
Reactions with Reactant in Limited Supply
Given 10 slices of cheese and 14 slices
of bread. How many sandwiches can
you make?
Balanced equation
1 cheese + 2 bread 1 sandwich
1 cheese ≡ 2 bread
1 cheese ≡ 1 sandwich
2 bread ≡ 1 sandwich
Reactions with Limited Reactants
Two methods can be used:
Product Method
Calculate the product from each starting material.
 The reactant giving the smallest number is limiting.
10 cheese x 1 sandwich = 10 sandwiches

1 cheese
14 bread x 1 sandwich = 7 sandwiches

2 bread
Correct answer
Bread is limiting. It will
be used up first
How much water will be produced by the combustion
of 25.0 g of H2 in the presence of 100. g of O2?
Write a balanced equation:
2 H2(g) + O2(g) 2 H2O(l)
1 mol H2
nH2 = 25.0 g = 12.40 mol H2
2.016 g
1 mol O2
nO2 = 100. g = 3.125 mol O2
32.00 g
2 H2 + O2 2 H 2O
Moles available: 12.40 3.125
How much water will be produced?
Product Method
Using H2
12.40 mol H2 (2H2O /2H2 ) = 12.40 mol H2O
Using O2
3.125 mol O2 (2 H2O /1 O2 ) = 6.250 mol H2O
O2 gave less water. O2 is limiting.
Base all calculations on O2
6.250 mol H2O x (18.02 g/ 1 mol ) = 113. g water
Consider :
4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g)
If 374 g of NH3 and 768 g of O2 are mixed, what mass
of NO will form?
Balanced equation? yes
nNH3 = 374 g 1 mol = 21.96 mol

17.03 g
1 mol
nO2 = 768g = 24.00 mol
32.00 g
4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g)
Mol available: 21.96 24.00
From NH3
NO formed: 21.96 mol NH3 4 NO = 21.96 mol NO
4 NH3
From O2
4 NO
NO formed: 24.00 mol O2 = 19.20 mol NO
5 O2
Smallest amount…. O2 is limiting.
Mass of NO formed?
4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g)
21.96 mol 24.00 mol 19.20 mol
O2 is limiting. Base all calculations on O2.
NO formed = 19.20 mol NO
Mass of NO = 19.20 mol NO x 30.01g = 576 g NO

1 mol
What mass of MgI2 is made by the reaction of 75.0 g
of Mg with 75.0 g of I2?
Mg + I2 → MgI2
• Balanced? YES
• Calculate moles
 75.0 g of Mg = 75.0g/(24.31 g mol-1) = 3.085 mol Mg
 75.0 g of I2 = 75.0g/(253.9 g mol-1) = 0.2955 mol I2
Limiting reactant? 1Mg ≡ 1I2 so I2 = limiting
• Since 1MgI2 ≡ 1I2 produce 0.2955 mol MgI2
• Mass of MgI2 = 0.2955 mol x 278.2 g/mol = 82.2 g
Percent Yield
Theoretical yield
The amount of product predicted by stoichiometry.
Actual yield
The quantity of desired product actually formed.
Percent yield
Actual yield
% yield = x 100%
Theoretical yield
Percent Yield
Few reactions have 100% yield.
Possible reasons
Side reactions may occur that produce undesired
product(s).
Incomplete reaction due to poor mixing or reaching

equilibrium…
Product loss during isolation and purification.
Percent Yield
You heat 2.50 g of copper with an excess of sulfur
and synthesize 2.53 g of copper(I) sulfide
16 Cu(s) + S8(s) 8 Cu2S(s)
What was the percent yield for your reaction?
1 mol
nCu used: 2.50 g = 0.03934 mol Cu
63.55g
16 mol Cu used  8 mol Cu2S made

Theoretical yield:
0.03934 mol Cu 8 Cu2S = 0.01967 mol Cu2S
16 Cu
Percent Yield
Heat 2.50 g of Cu with excess S8 and make 2.53 g of copper(I) sulfide:
16 Cu(s) + S8(s) → 8 Cu2S(s). What was the %-yield for your reaction?
Theoretical yield = 0.01967 mol Cu2S

159.2 g
= 0.01967 mol Cu2S = 3.131 g Cu2S
1 mol
Actual yield = 2.53 g Cu2S (in problem)
2.53 g
Percent yield = x 100% = 80.8%
3.131 g
PART II: Stoichiometry

Chemistry

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chemistry

Uploaded by

Copyright:

Available Formats

Engr. Edgie L.

 Nitrogen and oxygen

 Dry air is a convenient

 CO, NO2, O3, SO2, Pb, and Particulate Matter (PM)

 Commonly found throughout the country; cause a variety of

 High temperatures inside car engines cause oxygen

 Brown color of smog due to NO2; attacks lung

 Have much lower densities than solids or liquids.

 Have highly variable densities, depending on

 Mix with one another readily and thoroughly.

 Change volume dramatically with changing

 R is the universal gas constant.

 Atmospheric pressure is the force attributed to the

 As altitude increases, atmospheric pressure decreases.

 Each collision imparts a

 The height of the mercury

 These changes are determined empirically using gas

 Charles’s Law: relationship between T and V

 The empirical gas laws led to the ideal gas law

 Plots of V versus T for different gas samples converged to

 All of the fixed variables can be factored out as a new

 The unit for moles is always mol.

DALTON’S LAW OF PARTIAL PRESSURES

rate of ef f usionof A MMB

 The rate at which gas B escapes divided by the rate at which

 Gas laws do not depend on identity of gases.

 Pressure due to total moles gas present.

 The pressure exerted by a component of a gas mixture

 If the desired pressure is 750. torr, what should the

 If the gas is to be in a 15.0 L vessel held at 30°C, how

 Use mole ratios (stoichiometry)

 Connect number of moles of a gas to its temperature,

 For one mole of gas at STP, the standard molar volume is

 This number provides a conversion factor for

 Gases are composed of molecules that are widely separated

 Nonideal gas behavior can be explained using Kinetic

 Provides connections between observed macroscopic

 The average speed is proportional to the square root of the

 Mean free path decreases as pressure increases.

 Gas molecules are very close together.

 Therefore, volume of the gas particles becomes

 Gas molecules neither attract nor repel.

 Strength of attractive forces small compared to kinetic energy of gas

 Attractive and repulsive forces are significant under conditions of low

 Kinetic energy decreases with temperature.

 Gas molecules experience “sticky” collisions.

 Collision rate decreases, decreasing the pressure.

 a corrects for attractive forces.

 b corrects for the volume occupied by gas molecules.

 The van der Waals

 Both are zero in

 What is the percentage correction achieved by using

• At ordinary temperatures and pressures,

1. Molecules are much closer together in

 Schematic representation of the three

 Solids and liquids are condensed states.

 Liquids and gases are fluids.

 If we compare the strengths of interactions

 Intermolecular forces - the attractive and

 Dispersion forces are common to all

London Forces are very weak.

 In a group of Ar atoms the temporary

 Similar effects occur in a group of I2

• All substances have dispersion forces