AP

CHEMISTRY:
CHAPTERS 6
AND 17
NOTES
THERMODYNAMICS
6.1 THE NATURE
OF ENERGY
6.1 The Nature of Energy
• In this chapter, we will study
energy in terms of chemical
potential energy and how that
energy can change form to
accomplish work. We will
focus specifically on
thermochemistry, which
involves heat and energy
transfer.
ENERGY AND
WORK

• Energy- the capacity to do work or to

produce heat
• Work- force acting over a distance (Work =
Fd)
– It involves a transfer of energy
The 1 st LAW OF THERMODYNAMICS:
LAW OF CONSERVATION OF ENERGY
• 1st Law of Thermodynamics- also known
as the Law of Conservation of Energy.
• States that energy can be converted from
one form to another but it can be neither
created nor destroyed.
– The total amount of energy in the universe is
constant.
Energy can be
classified in two
ways:
• Potential energy- energy due to position or composition
(included chemical potential energy)
– KE = ½ mv2
– m = mass in kg
– v = velocity in m/s
– units are J, since J = (kg.m2)/s2
• Kinetic energy- energy due to the motion of an object
– Kinetic energy is dependent on the mass and velocity of an object
 Heat

• Heat- (q) involves a transfer of energy

between two objects due to a temperature
difference.
– Heat always moves from warmer matter to cooler
matter.
 SYSTEM VS
SURROUNDINGS

• In this chapter, we will describe where heat moves

and will use the terms system and surroundings.
• In terms of a chemical reaction, the system is our
reaction.
• The surroundings are everything else, including
things like the container the reaction occurs in, the
room it sits in, etc.
 TEMPERATURE

• Temperature- a property that reflects random

motions of the particles of a particular
substance
– Exothermic- reaction which releases heat
• Energy flows out of the system
• Potential energy is changed to thermal energy
• Products have lower potential energy than reactants
ENDOTHERMIC

• Reaction which absorbs heat

• energy flows into the system
• thermal energy is changed into
potential energy
• products have higher PE than reactants
THE VALUE OF “E”
• Internal energy (E) of a system is the sum of the
kinetic and potential energies of all the particles in a
system.
• Thermodynamic quantities always consist of a
number and a sign (+ or -). The sign represents the
system’s point of view. (Engineers use the
surrounding’s point of view)
– Exothermic -E (systems energy is decreasing)
– Endothermic +E (systems energy is increasing)
CALCULATING THE ENERGY
IN A SYSTEM E = q + w
 E is the change in the system’s internal
energy
 q represents heat
 w represents work usually in J or kJ
 

• Example: Calculate E if q = -50 kJ

and w = +35kJ.
DE = q + w
= -50 kJ + 35 kJ
= -15 kJ
Work on
Gases

Units come from: 1L.atm = 0.001m3.101,325 Pa

(1 Pa = N/m2), so 101.325 N.m or J

• For a gas that expands or is compressed, work can

be calculated by:
– w = - PV
– units: L.atm
Example: Calculate the work if the
volume of a gas is increased from
15 ml to 2.0 L at a constant
pressure of 1.5 atm.

• w = -PDV
• w = -1.5 atm (1.985L)
• w = -3.0 L . atm
PRACTICE QUESTION
One version of the first law of thermodynamics is
expressed as ∆E = q + w
Which gives the sign convention for this relationship that
is usually used in chemistry?

Heat, q Heat, q Work, w Work, w,

Added to added to the done on done on the
the surroundings the surroundings
system system

A) - + - -
B) + + + +
C) + + + -
D) + - + -
E) + - - -
LET’S TALK LAB…

• Solve for the calorimeter constant and write this on your cup. Be sure
to hang on to your cup!
• Solve for q=mCΔT for the solid you used. The mass used is the solid
and the liquid mass. The specific heat used is for water.
• Discuss your procedures for Thursday with your lab partner. You
determine how you will calculate the amount of heat lost or gained
by an entire cold pack.
 LAB DATA
Compound Heat of Solution Heat of Solution Avg. Heat of
Name Group 1 Group 2 (if tested) Solution (if tested
twice)

NaCl

CaCl2

NaC2H3O2

Na2CO3

LiCl

NH4NO3
6.2 ENTHALPY
AND
CALORIMETRY
Enthalpy
• Enthalpy (H) concerns the heat • H = E + PV
energy in a system. – E is internal energy
• H = q at constant pressure – P is pressure
only – V is volume
– Reactions that do not involve
gases or where moles of gases
do not change are considered “at
constant pressure”.
• At constant pressure, the terms
heat of reaction and change in
enthalpy are used
interchangeably.
Enthalpy Change in a
System
• The change in the enthalpy
of a system can be
calculated using:
– H= ΣmH products - ΣnH
reactants
• For an exothermic reaction,
H is negative
• For an endothermic reaction,
H is positive
EXAMPLE: Sulfur dioxide reacts with oxygen. Write the balanced
equation for the reaction of one mole of sulfur dioxide,
calculate the enthalpy value for the reaction, the draw an
energy diagram for this reaction based on your answer. Be sure
to label reactants, products, and the enthalpy of the system.

• Balanced Equation
SO2 + ½O2  SO3
• Enthalpy Value
H= ΣmH products - ΣnH reactants
H= [-395.7kJ/mol] - [-296.8kJ/mol + ½ 0] = -98.9 kJ/mol
• Energy Diagram
THERMODYNAMIC EQUATIONS
• For many reactions, a value is given alongside a
balanced equation called a thermochemical
equation. This value should be associated with
the moles of each substance given in the problem.
– 1/8 S8(s) + O2(g)  SO2(g) H = -296.8 kJ
– As you can see, 1/8 mole of sulfur would release this
amount of energy while one mole of sulfur would
release eight times that amount of energy.
Example: For the reaction
2Na + 2H2O  2NaOH + H2 , H = -368 kJ
Calculate the heat change that occurs when 3.5 g of
Na reacts with excess water.

• 3.5g Na 1 mol Na -368 kJ =

• 22.99g Na 2 mol Na
• DH = -28 kJ (or say 28 kJ are released)
PLEASE HAVE YOUR NOTES
OUT ON YOUR DESK. 
• Today we will do some quick notes before you
begin your lab. You will have plenty of time,
don’t worry!
• HW 1 and 2 will be checked tomorrow.
CALORIMETRY
Heat Capacity (C)
C = heat absorbed
Increase in temp.
C = J/g°C or J/mol°C
• Calorimetry- the science of
measuring heat flow in a
chemical reaction.
– It is based on observing the
temperature change when a body
absorbs or discharges heat.
– The instrument used to measure
this change is the calorimeter.
Here are some
helpful tables that
are found in the back
of your text book.
 q = mCT
CALORIMETRY J = (J/g°C )(g)(°C)

• Constant pressure calorimetry- pressure remains

constant during the process
– Constant pressure calorimetry uses a set up called a
coffee cup calorimeter
• The primary reaction to calculate heat changes in a
system is the “Mcat” equation.
– Energy released as heat = (heat capacity) (mass of
solution ) (increase in temp)
Example: A coffee cup calorimeter contains 150 g H 2 O
at 24.6 o c. A 110 g block of molybdenum is heated to
100 o c and then placed in the water in the calorimeter.
The contents of the calorimeter come to a temperature
of 28.0 o c. What is the heat capacity per gram of
molybdenum?

• qwater = mCΔT and qwater = qMo

• So… mwCw ΔTw = mMoCMo ΔTMo
• (150g)(4.18J/goC)(3.4oC) = (110g) (CMo)(72oC)
• CMo = 0.27J/goC
100.0 ml of 0.100M silver nitrate is mixed with 100.0 ml
of 0.200M sodium chloride. Both solutions start at
room temperature (25.0°C) and, once combined into a
coffee cup calorimeter, the final temperature reading
after mixing is 26.8°c. Find the heat of reaction in
kj/mol of silver nitrate.

• AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq)

• q = mCΔT = (200.0g)(4.18 J/g°C)(1.8°C)

• q = 1500 J or 1.5 kJ

• (0.1000L)(0.100M AgNO3) = 0.0100 mol AgNO3 in the

reaction
• 1.5kJ/0.0100mol = 150 kJ/mol
EXTENSIVE VS INTENSIVE
PROPERTIES • Let’s Practice!
• The number of calories of energy
• In terms of calorimetry, E
you derive from eating a banana
we can describe certain • The number of calories of energy
properties of the made available to your body I
reaction as an: when you consume 10.0 g of
I sugar I
– Extensive property- this
depends on the amount • The density of your blood
of substance (ex. Heat • The mass of iron present in
E
of reaction) blood
• The electrical resistance of a
– Intensive property- I
doesn’t depend on the
piece of 22-gauge copper wire.
amount of substance
• The melting point of copper
wire. I
(ex. Temperature)
CALORIMETRY CAN ALSO BE DONE
IN A CLOSED, RIGID CONTAINER.
• This is called constant volume
calorimetry
– Ex. Flashbulb in a camera or a bomb
calorimeter
– No work can be done since the volume
doesn’t change
– Heat evolved = T x heat capacity of
calorimeter (energy required to change
the temp 1oC)
6.3 HESS’S LAW
 HESS’S LAW
• Hess’s Law- States that the change in enthalpy
from products to reactants, or H, is the same
whether the reaction occurs in one step or in
several steps.
– H is not dependent on the reaction pathway.
– The sum of the H for each step equals the H for the
total reaction.
– If a reaction is reversed, the sign of H is reversed.
– If the coefficients in a reaction are multiplied by an
integer, the value of H is multiplied by the same
integer.
HESS’S LAW APPLIED

N2 + O2  2NO
2NO + O2  2NO2 N2 + 2O2  2NO2
Example: given the following reactions and
their respective enthalpy changes, calculate
H for the reaction: 2C + H 2  C 2 H 2 .

C2H2 + 5/2 O2  2CO2 + H2O H = -1299.6 kJ/mol C2H2

C + O2  CO2 H = -393.5 kJ/mol C

H2 + ½ O2  H2O H = -285.9 kJ/mol H2

• 2C + 2O2  2 CO2 H = 2(-393.5) kJ

• H2 + ½ O2  H2O H = -285.9 kJ
• 2CO2 + H2O  C2H2 + 5/2 O2 H = +1299.6 kJ
• 2C + H2 C2H2  H = 226.7kJ
Example: the heat of combustion of C to CO 2 is -
393.5 kJ/mol of CO 2 , whereas that for
combustion of CO to CO 2 is -283.0 kJ/mol of CO 2 .
Calculate the heat of combustion of C to CO.
• First, write the equations given, as well as your goal
equation.
• Goal: C + ½O2  CO
• Given: C + O2  CO2 DH = -393.5 kJ
CO + ½ O2  CO2 DH = -283.0 kJ
• Now, rearrange to find the goal equation!
• C + O2  CO2 DH= -393.5 kJ
• CO2  CO + 1/2 O2 DH= +283.0 kJ
• C + 1/2O  CO DH= -110.5 kJ
6.4 STANDARD
ENTHALPIES OF
FORMATION
ΔH F°
• Standard enthalpy of formation ()
• The change in enthalpy that accompanies the
formation of one mole of a compound from its
elements with all substances in their standard
states at 25oC.
• The degree sign on a thermodynamics function
indicates that the process it represents has been
carried out at standard state conditions.
STANDARD STATE CONDITIONS
• for gases, pressure is 1 atm
• for a substance in solution, the concentration is 1 M
• for a pure substance in a condensed state (liquid or solid), the
standard state is the pure liquid or solid.
• for an element, the standard state is the form in which the
element exists under conditions of 1 atm and 25oC.
• Values of are found in Appendix 4 and at the end of these
notes
• reaction = products - reactants
Example: The standard enthalpy
change for the reaction
CaCO 3 (s)  CaO + CO 2 (g) is 178.1 kJ.
Calculate the for CaCO 3 (s).
• Solve for the heat of a single compound by using
reaction = products - reactants

• 178.1 kJ = [-635 kJ + -393.5] - [x]

• X = -1207 kJ
6.5 Present Sources of
Energy
• In this section, we will discuss some sources of
energy, including fossil fuels, and their effects on
the environment.
PETROLEUM
• Petroleum- A thick, dark liquid composed of
hydrocarbons chains of 5-25 carbons
– Refining petroleum involves the process of pyrolytic
cracking, or distilling the fractions of petroleum from
the main sample based on their molecular mass and
boiling point.
GASOLINE
• Gasoline C5-C12
– Gasoline, when first used in car engines, caused a
dramatic knocking sound and was thus treated with
tetraethyl lead, (C2H5)4Pb, an antiknock agent. This
introduced lead into the atmosphere as the fuel was
spent and increased the amount of ingested lead in the
human and animal populations until 1960 when
“leaded” gas was finally phased out.
– kerosene & jet fuel C10-C18
– heating and lubricating oil and diesel fuel C15-C25
– asphalt >C25
NATURAL GAS
• Natural gas- This
substance is usually
found alongside
petroleum and is
composed mostly of
methane. It also
contains ethane,
propane, and butane.
Coal

• Coal- formed from the remains of plants

buried under pressure for many years.
Cellulose, CH2Ox, gradually loses its H
and O.
• Coal develops through 4 stages:
– lignite (least valuable)
– subbituminous
– bituminous (high sulfur)
– anthracite (most valuable)
• Coal provides 20% of our energy in the
U.S.
CO 2 and the Environment

• Effects of CO2 on the Climate

• Greenhouse effect - H2O and CO2 molecules in the
atmosphere reflect IR radiation and send it back to earth thus
raising the earth’s temperature.
• The CO2 concentration has increased by about 16% in the
past 100 years because of increase in the use of fossil fuels.
NEW
ENERGY
SOURCES

• Coal gasification- treating coal with oxygen and steam at high

temperatures to break down many of the C-C bonds and form C-O and
C-H bonds.
• The products are syngas (CO + H2) and methane gas. Syngas may be
converted to methanol.
– CO(g) + 2H2(g)  CH3OH(l)
 NEW ENERGY SOURCES
• Hydrogen as a Fuel
• H2 (g) + ½O2(g)  H2O(l)

• Ho = -286 kJ
– ~2.5 times the energy of
natural gas
– 3 problems: production (too
expensive), transport (too
volatile), and storage (large
volume, decomposes to H
atoms on metal surfaces,
makes metal brittle-forms
metal hydrides)
OTHER ALTERNATIVES:

• oil shale
• ethanol
• gasohol
• seed oil
(sunflower)
CHAPTER 17: Spontaneity,
Entropy and Free Energy
17.1 & 17.2
SPONTANEOUS
PROCESSES AND
ENTROPY AND THE
SECOND LAW OF
THERMODYNAMICS
1 Law of
st

Thermodynamics
• The first Law of Thermodynamics states that energy is
neither created nor destroyed; it is constant in the universe.
We can measure energy changes in chemical reactions to
help determine exactly what is happening and how it is
occurring.
• Keep in mind that thermodynamics deals with the
reactants and products while kinetics deals with how
reactants become products.
SPONTANEOUS… WHAT??

• Spontaneous process-
occurs without outside
intervention (ex. Rusting)
– This may be fast or slow
(CO2 sublimes at room
temperature vs. iron rusting
when in the presence of
oxygen)
 ENTROPY
Entropy!
Low

Entropy!
High
• Entropy (S)- a measure of randomness or disorder
– This is associated with probability. (there are more ways for
something to be disorganized than organized)
– Entropy increases going from a solid to a liquid to a gas and when
solutions are formed.
– Entropy increases in a reaction when more atoms or molecules are
formed.
– Entropy increases with increasing temperature.
ENTROPY INCREASES…

• SLG

• More molecules
produced
• Temperature
increases
 2 LAW OF
ND

THERMODYNAMICS
• 2nd Law of
Thermodynamics- In any
spontaneous process there
is always an increase in the
entropy of the universe.
The energy of the universe
is constant but the entropy
of the universe is
increasing.
17.3 & 17.4
ENTROPY AND
FREE ENERGY
FREE ENERGY
G = H -TS
• Free energy (G)- the amount of energy
available to do work.
– Free energy change is a measure of the
spontaneity of a reaction. It is the maximum
work available from the system.
• A spontaneous reaction carried out as
constant temperature and pressure has a
negative G. For example, when ice melts
H is positive (endothermic), S is positive
and G = 0 at 0˚C.
 G = H -TS

S H G Spontaneous?

+  -  -  Yes, always
+  +  ?  Yes, at high T

-  -  ?  Yes, at low T

+  +  +  No, never
17.5 ENTROPY
CHANGES IN
CHEMICAL
REACTIONS
3 LAW OF
RD

THERMODYNAMICS

• Third Law of Thermodynamics- The entropy of a

perfect crystal at 0 K is zero.
• Any substance that is not at 0 Kelvin must have a
value for entropy! This sets entropy apart for
enthalpy. Enthalpy values are just changes, while
entropy values are absolute and cannot drop below
zero.
 Ex. Given the following standard
molar entropies, calculate S o for
the reaction:
2Al(s) + 3MgO(s)  3Mg(s) + Al 2 O 3 (s)

• Mg(s) = 33.0 J/K Al2O3(s) = 51.0 J/K

• Al(s) = 28.0 J/K MgO(s) = 27.0 J/K

• Soreaction = Soproducts - Soreactants

• So = [3(33.0J/K) + 51.0J/K] – [2(28.0J/K) +
3(27.0J/K)]
• So = 13.0 J/Kmol.rxn
17.6 FREE
ENERGY AND
CHEMICAL
REACTIONS
The Standard Free Energy
Change
• Standard free energy change (G°) -The change in
free energy that occurs if the reactants in their
standard states are converted to products in their
standard states.
– G° =Gfoproducts - Gforeactants at standard conditions
– Gfo for a free element in its standard state is zero.
EX. GIVEN THE EQUATION N 2 O 4 (G)
 2NO 2 (G) AND THE FOLLOWING
DATA, CALCULATE G O .
• Gfo for N2O4(g) = 97.82 kJ/mol,
• Gfo for NO2(g) = 51.30 kJ/mol

• Go = [2(51.30kJ/mol)] – [ 97.82 kJ/mol]

• = 4.78 kJ/mol rxn
THE GIBBS-HELMHOLTZ
EQUATION
• The Gibbs-Helmholtz equation works like
the Gibbs Free Energy equation, just at
standard state conditions.
– Go =Ho -TSo
– (When working this, change the units for S to
kJ).
Ex. For the given reaction and the
following information, calculate G o
at 25°C.
2PbO(s) + 2SO 2 (g)  2PbS(s) + 3O 2 (g)
  Ho (kJ/mol) So (J/mol.K)
PbO (s) -218.0 70.0
SO2 (s) -297.0 248.0
PbS (s) -100.0 91.0
O2 (g) ? 205.0

Ho = [2(-100.0) + 3(0)]- [2(-218.0) + 2(-297.0)]

= 830.0 kJ/mol rxn
So = [2(91.0) + 3(205.0)] – [2(70.0)+2(248.0)]
= 161.0 J/K.mol rxn = 0.1610 kJ/mol
Go = Ho - T So
Go= 830.0 kJ/mol -298K(0.1610 kJ/mol)
= 782 kJ/mol rxn
17.7 THE
DEPENDENCE OF
FREE ENERGY
ON PRESSURE
ENTROPY AND PRESSURE/
VOLUME
• In an ideal gas, enthalpy does not
depend on pressure. Entropy,
however, does depend on pressure
because it depends upon volume.
– Gases in large volumes have greater
entropy than in a small volume.
– Gases at a low pressure have greater
entropy than at a high pressure.
• Because entropy depends on
pressure, G of an ideal gas
depends on its pressure.
17.7 The Dependence of Free
Energy on Pressure
 If we incorporate PV = nRT with the equation for
free energy, we end up with an equation to
calculate free energy in relation to temperature
and pressure variables.

G = G° + RT ln (Q)
• Q = reaction quotient (partial pressure of
products/reactants raised to the power of their
coefficients)-only pressures of gases are included.
• T = temperature in Kelvin
• R = gas constant 8.3145 J/K.mol
• G° = free energy change at 1 atm (be sure to change
to Joules!)
 Ex. Calculate G at 298K for the
following reaction if the reaction mixture
consists of 1.0 atm N 2 , 3.0 atm H 2 , and 1.0
atm NH 3 .
• N2(g) + 3H2(g)  2NH3(g) Go = -33.32 kJ/mol
• G = Go + RT lnQ
• G = -33,320J/mol + 8.314J/Kmol(298K) ln
• G = -41,500J/mol rxn or
• -41.5 kJ/mol rxn
17.8 FREE
ENERGY AND
EQUILIBRIUM
FREE ENERGY AND
EQUILIBRIUM
• The equilibrium point in
terms of kinetics occurs
when the forward and
reverse reactions were
occurring at an equal rate.
• In terms of free energy, the
equilibrium point occurs at
the lowest value of free
energy available to the
reaction system.
FREE ENERGY AND
EQUILIBRIUM
• These two definitions are the same!
– G = Gproducts - Greactants = 0
• If a process has just shifted from nonspontaneous to
spontaneous, then at the point where it changes, the value for
G is zero. If G is zero, then Ho = TSo.
Ex. Given for the reaction Hg(l)  Hg(g)
that H o = 61.3 kJ/mol and S o = 100.0
J/mol . K, calculate the temperature of the
normal boiling point of Hg.

• Go =Ho -T So

• G = 0 at phase change
• 0 = 61.3 –T(0.1000)
• T = 613K or 340oC
THE “RAT LINK” EQUATION
• We can utilize the previous two equations (G = Gproducts -
Greactants = 0) and (G = Go + RT ln (Q)) to form an
equation that describes the relationship between free energy
and the value of the equilibrium constant.
• Go = -RT ln(K) (the “rat link” equation)
– When Go = 0, free energy of reactants and products are equal when
all components are in their standard states. During a phase change,
G = 0.
– When Go < 0, Go products < Go reactants The reaction is not at
equilibrium, K > 1 since pressure of products is > 1 and the pressure
of reactants is < 1.
– When Go > 0, Go reactants < Go products The reaction is not at
equilibrium, K < 1 since pressure of products is < 1 and the pressure
Ex. Calculate the approximate standard
free energy for the ionization of
hydrofluoric acid, HF (K a = 1.0 x 10 -3 ), at
25 o C.

• Go = -RT ln K
• Go = -8.314(298)ln (1.0 x 10-3)
• = 1.7 x 104J or 17 kJ
FREE ENERGY AND
EQUILIBRIUM
• We can use G =Go +
RT ln(Q) to calculate the
direction that a reaction
will shift to reach
equilibrium.
– Free energy is energy
available to do useful
work. Wmax = G