Chapter 5 Thermo 1

Energy & Chemistry

Chapter 5 Questions that need to be addressed:
How do we measure and calculate the energy
Principles of Chemical changes that are associated with physical changes
Reactivity: and chemical reactions?
Energy and Chemical
What is the relationship between energy changes,
Reactions
heat, and work?
How can we determine whether a chemical reaction is
product-favored or reactant-favored at equilibrium?
How can we determine whether a chemical reaction
or physical change will occur spontaneously, that is,
Jeffrey Mack without outside intervention?
California State University,
Sacramento

Units of Energy Energy & Chemistry

1 calorie = heat required to raise Some Basic Principles
temp. of 1.00 g of H2O by 1.0 C.
Energy as the capacity to do work or transfer heat (q).
1000 cal = 1 kilocalorie = 1 kcal
Heat (q) is NOT temperature, temperature is a
1 kcal = 1 Calorie (a food measure of kinetic energy.
calorie) Energy is divided into two basic categories:
Kinetic energy (the energy associated with motion)
SI units for energy: joule (J)
Potential energy (energy that results from an objects position).
1 cal = exactly 4.184 J The law of conservation of energy requires that
James Joule energy can neither be created nor destroyed.
1818-1889
However, energy can be converted from one type into
another.

Energy & Chemistry Potential & Kinetic Energy

Energy can be divided into two forms: Kinetic energy energy of motion
Kinetic: Energy of motion: Translation
Thermal
Mechanical
Electrical

Potential: Stored energy:

Gravitational
Electrostatic
Chemical & Nuclear
Chapter 5 Thermo 2

Potential & Kinetic Energy Energy & Chemistry

Potential energy energy a motionless body
has by virtue of its composition and position.

Burning peanuts Burning sugar

supply sufficient (sugar reacts with
energy to boil a KClO3, a strong
cup of water. oxidizing agent)

Thermal Equilibrium System & Surroundings

SYSTEM
The object under study
SURROUNDINGS
Everything outside the
system
Energy transfer as heat will occur spontaneously from an Energy flows between
object at a higher temperature to an object at a lower the two
temperature.
Transfer of energy as heat continues until both objects are at
the same temperature and thermal equilibrium is achieved.
At thermal equilibrium, the object with a temperature
increase has gained thermal energy, the object with a
temperature decrease has lost thermal energy.

Directionality of Energy Transfer Directionality of Energy Transfer

When energy leaves the system and goes into the
surroundings, the process is said to be
EXOTHERMIC.
In the case of thermal energy, the temperature of
the system decreases. (qsystem < 0)
Tsystem = (Tfinal Tinitial) < 0
When energy enters the system and from the
surroundings, the process is said to be
ENDOTHERMIC.
In the case of thermal energy, the temperature of
the system increases. (qsystem > 0)
Tsystem > 0
Chapter 5 Thermo 3

Heat & Changes in Internal Energy Heat & Changes in Internal Energy

Heat flows between the system and Usystem = Ufinal - Uinitial = q

surroundings.
U is defined as the internal energy of the If heat enters the system:
system.
U > 0 therefore q is positive (+)
q = the heat absorbed or lost
If heat leaves the system:
Usystem = Ufinal - Uinitial = q U < 0 therefore q is negative ()

The sign of q is a convention, it designates the

direction of heat flow between the system and
surroundings.

Heat & Changes in Internal Energy Heat Capacity

Usystem = Ufinal - Uinitial = q When heat is absorbed or lost by a body, the
temperature must change as long as the phase
(s, g or l) remains constant.
Surroundings
Usystem

The amount of heat (q) transfer related to an object

heat in and temperature is given by:
Usystem

heat out

q = C DT
System
J
qsystem > 0 qsystem < 0 C or K

(+) ()
Usystem > 0 Usystem < 0 q = heat lost or gained (J)
increases decreases
C = Heat Capacity of an object
q = the heat absorbed or lost by the system. T = Tfinal Tinitial is the temperature change (C or K)

Heat & Specific Heat Capacity Does it matter if we calculate a temperature

change in Kelvin or degrees C?
When heat is absorbed or lost by a body, the
temperature must change as long as the phase (s, g or l)
remains constant. let Tin = 25.0 C and Tf = 50.0 C
The amount of heat (q) transfer per unit mass of a
Recall that T = Tf Tin
substance is related to the mass and temperature by:

q = m C DT Tf = 50.0 C = 50.0 C + 273.2 = 323.2 K

Tin = 25.0 C = (25.0 C + 273.2) = 298.2 K

q = heat lost or gained (J) m = mass of substance (g)

J T = 25.0 C T = 25.0 K
C = the Specific Heat Capacity of a compound
g C or K The are the same!
T = Tfinal Tinitial is the temperature change (C or K)
Chapter 5 Thermo 4

Determine the final temperature of a 25.0 g block of Determine the final temperature of a 25.0 g block of
metal that absorbs 255 cal of energy. The initial metal that absorbs 255 cal of energy. The initial
temperature of the block was 17.0 C J temperature of the block was 17.0 C J
2.72 2.72
The specific heat capacity of the metal is: g C The specific heat capacity of the metal is: g C
Strategy Map: Find T of the metal after
final
q = m C DT = m C (Tfinal - Tinitial )
it absorbs the energy
q
Data Information: Mass, rearranging: Tfinal = +Tinitial
initial temp, heat capacity mC
of metal, heat (q) absorbed.
4.184 J
+255 cal
Solve q = mCT for Tfinal, 1 cal
plug in data. Tf = + 17.0 C =32.7
J
25.0 g 2.72 C
Final temperature of the g C Tf > Tin
metal is determined. as
expected

Example Problem: Example Problem:

55.0 g of iron at 99.8 C is placed into into 225 g water at 55.0 g of iron at 99.8 C is placed into into 225 g water at
initially at 21.0 C. initially at 21.0 C.
At thermal equilibrium, the water and iron are both at 23.1 C At thermal equilibrium, the water and iron are both at 23.1 C
What is the specific heat capacity of the metal? What is the specific heat capacity of the metal?

Solution:
Heat is transferred from the hot metal to the colder
water.
Energy is conserved so:
qFe + qwater = 0
qFe = -qwater

Example Problem: Example Problem:

55.0 g of iron at 99.8 C is placed into into 225 g water at 55.0 g of iron at 99.8 C is placed into into 225 g water at
initially at 21.0 C. initially at 21.0 C.
At thermal equilibrium, the water and iron are both at 23.1 C At thermal equilibrium, the water and iron are both at 23.1 C
What is the specific heat capacity of the metal? What is the specific heat capacity of the metal?

Solution: Solution:

qFe + qwater = 0
-mwater Cwater DTwater
qFe = -qwater CFe =
mFe DTFe
mFe CFe DTFe = -mwater Cwater DTwater
Chapter 5 Thermo 5

Example Problem: Energy & Changes of State

55.0 g of iron at 99.8 C is placed into into 225 g water at
initially at 21.0 C.
At thermal equilibrium, the water and iron are both at 23.1 C
What is the specific heat capacity of the metal?

Solution:

J 1K
225 g 4.184 (23.1 C 21.0 C)
gK 1 C J
CFe 0.469 When matter absorbs heat, its temperature will rise until
55.0 g (23.1 C 99.8 C)
1K gK
1 C it undergoes a Phase Change.
The matter will continue to absorb energy, however
during the phase change its temperature remains
constant: Phase changes are Isothermal processes.

Energy Transfer & Changes of State Energy Transfer & Changes of State

Some changes of state (phase Some changes of state (phase

changes) are endothermic: changes) are exothermic:
When you perspire, water on your When it is muggy outside, water
skin evaporates. condenses on your skin.
This requires energy. This releases energy.
Heat from your body is absorbed by Heat from condensation is absorbed
the water as it goes from the liquid + energy by your skin as water in the vapor + energy
state coverts to the liquid state.
state to the vapor state, as a result
you cool down. As a result you feel hot.

H2O(l) + Heat H2O(g)

H2O(g) H2O(l) + Heat

Heating/Cooling Curve for Water Heat & Changes of State

Note the isotherms The energy associated with a change of state is given by the
at each phase Enthalpy or Heat of the phase change.
transition. Since there is no temperature change associated with the
process, the units are most often in J/g or J/mol.

Sublimation: subH > 0 (endothermic)

Vaporization: vapH > 0 (endothermic)
Melting or Fusion: fusH > 0 (endothermic)
Deposition: depH < 0 (exothermic)
Condensation: conH < 0 (exothermic)
Freezing: freH < 0 (exothermic)

Where H refers to the Heat of a phase change

Chapter 5 Thermo 6

Energy Change Calculations Problem:

What quantity of heat is required to melt 500. g
Heating & Cooling: of ice at 0 C then heat the resulting water to
steam at 100 C?
q(heating or cooling) = m C T

Heat absorbed or lost in a Phase change: +333 J/g +2260 J/g

q(phase change) = (phase change)H n

melt the ice form liquid water at 0 C heat the water to 100 C boil
water
(n = moles or grams)
fusH Cwater VapH

Problem: Problem:
What quantity of heat is required to melt 500. g What quantity of heat is required to melt 500. g
of ice at 0 C then heat the resulting water to of ice at 0 C then heat the resulting water to
steam at 100 C? steam at 100 C?

Constants Needed: Ice water water steam

Equations:
H2O(s) fusH H2O(l) Cwater H2O(l) vapH H2O(g)
J (0 C) (0 C) (100 (100
Heat of fusion of ice = 333 qphase change =
g mH C) C)
J
Specific heat of water = 4.18 qheat = mCT
gK
J
Heat of vaporization = 2260
g

Problem: Problem:
What quantity of heat is required to melt 500. g What quantity of heat is required to melt 500. g
of ice at 0 C then heat the resulting water to of ice at 0 C then heat the resulting water to
steam at 100 C? steam at 100 C?

Ice water water steam Ice water water steam

H2O(s) fusH H2O(l) Cwater H2O(l) vapH H2O(g) H2O(s) fusH H2O(l) Cwater H2O(l) vapH H2O(g)
(0 C) (0 C) (100 (100 (0 C) (0 C) (100 (100
C) C) C) C)
J
melt ice heat water boil water
qtotal 500. g 333
g
J
500. g 4.18 (100.0 C 0.0 C)
qtotal = q1 = nice D fusH + q2 = mwater Cwater DT + q3 = nwater D vapH g C
J
500. g 2260 1.51 10 6 J
g
Chapter 5 Thermo 7

First Law of Thermodynamics First Law of Thermodynamics

The total internal energy of an isolated system is constant.
The system is that which we are
interested in.
The surroundings are
everything in contact with the
system.
Any energy lost by the
system is transferred to the
surroundings and vice versa.
Energy Any change in energy is
related to the final and initial
states of the system.
Energy

Together:
System + Surroundings = Universe Usystem = Ufinal Uinitial
The same holds for the surrounding!

Relating U to Heat and Work

energy transfer in energy transfer out
Energy cannot be created or destroyed. (endothermic), +q (exothermic), -q
Energy of the universes (system + surroundings) is constant.
Any energy transferred from a system must be transferred to
the surroundings (and vice versa).
From the first law of thermodynamics: When a system undergoes
SYSTEM
a physical or chemical change, the change in internal energy is
given by the heat added to or absorbed by the system plus the U = q + w
work done on or by the system:

U q w
change in heat
system = lost or gained +
work done by or w transfer in w transfer out
on the system (+w) (-w)
energy by the system

work and Energy is the capacity to do work.

Energy in Energy out Work equals a force applied through a distance.
heat can
balance! When you do work, you expend energy.
Uf > Ui Uf < Ui
U Final U initial When you push down on a bike
pump, you do work.
work in Work work out force force
P= =
x2
energy

area
change in volume V = x3
F
q in Heat q out P V = x3 = F x
x2
U initial U Final P V = work

Usystem > Usystem < Therefore work is equal to a change

Usystem = 0 of volume at constant pressure.
0 (+) 0 ()
Chapter 5 Thermo 8

Enthalpy Enthalpy is a State Function

Enthalpy, H is the heat transferred between the system and
surroundings under conditions of constant pressure.
No matter which path is taken
(AB) the results are the B
H = qp the subscript p same:
indicates constant Final Initial
H = U + PV pressure
Since individual Enthalpies
A
DH = D (U + PV ) cannot be directly measured,
we only deal with enthalpy
if no PV work is = DU + PDV changes
(H = Hf Hi)
0 the change in
done by the system, enthalpy is the
V = 0
H = Up change in internal
energy at constant For a system the overall change in Enthalpy is path
pressure independent.

Enthalpies & Chemical Reactions:

Enthalpy Conditions
rH
Since Enthalpies are state functions, one Reactants Products
must specify the conditions at which they are H = Hfinal Hinitial
measured.
Enthalpy of reaction = rH = Hproducts Hreactants
H(T,P): Enthalpy is a function of temperature
and pressure.
H (Products) H (Reactants)
H indicates that the Enthalpy is taken at
Standard State conditions. rH < 0
Energy

rH > 0
Standard State Conditions are defined as:
1 atm = 760 mm Hg or 760 torr & 298.15 K or H (Reactants) H (Products)
Exothermic
25 C Endothermic

Thermochemical Equations Problem:

How many kJ of energy are released when 128.5 g of
Just like a regular chemical equation, with an energy term. methane, CH4(g) is combusted?

CH4(g) + 2O2(g) CO2(g) + 2H2O(g) rHo = 802 kJ

CH4(g) + 2O2(g) CO2(g) + 2H2O(g) rHo = 802 kJ
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) + 802 kJ

energy out g mols J

Energy is a product just like CO2 or H2O!
Exothermic
molar Reaction
What does this imply? CONVERSION FACTORS!!! mass enthalpy
From the equation:
1 mol CH4 1 mol rxn +802 kJ
128.5g CH4 = 6.43103 kJ
+802 kJ of Energy Released +802 kJ of Energy Released 16.04 g 1 mol CH4 1mol rxn
1 mol CH4 (g) consumed 2 mol H2O (g) produced
Chapter 5 Thermo 9

Thermochemical Equations Thermochemical Equations

When the reaction is reversed , the sign of H reverses:
CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
H scales with the reaction:
1 1
[ CH4(g) + 2O2(g) CO2(g) + 2H2O(g)] [rHo = 802 kJ]
2 2
rHo = 802 kJ
Exothermic
1 1
CH4 (g) + O2 (g) CO2 (g) + H2O(g) rHo = 401 kJ
2 2

CO2(g) + 2H2O(g) CH4(g) + 2O2(g) rHo = +802 kJ

Yes you can write the reaction with fractions, so long as
Endothermic you are writing it on a mole basis

Thermochemical Equations Comparing the reaction with water as a gas or

liquid:
CH4(g) + 2O2(g)
Change in enthalpy depends on state:
reactants

CH4(g) + 2O2(g) CO2(g) + 2H2O(g) rH = 802 kJ rHo = 802 kJ either pathway

Enthalpy (H)

gives the same

results!
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) rH = 890 kJ
products rHo = 890 kJ
= 88kJ CO2(g) + 2H2O(g)
From your text: This means that waters liquid state lies The difference is the
44 kJ/mol lower than the gas state 88 kJ released when 2
H2O(g) H2O(l) mols of water go from 2 44 kJ
products
The difference in the rxn H gas to liquid.
[ H = 44 kJ/mol ] 2 =
88kJ CO2(g) + 2H2O(l)
is due to the change in state!!

Constant Pressure Calorimetry, Constant Pressure Calorimetry,

Measuring H Measuring H
A constant pressure The constant pressure
calorimeter can be used calorimeter used in general
to measure the amount of chemistry laboratories is
energy transferred as often a coffee-cup
heat under constant calorimeter. This
pressure conditions, that inexpensive device
is, the enthalpy change consists of two nested
for a chemical reaction. Styrofoam coffee cups with
a loose-fitting lid and a
temperature-measuring
device such as a
thermometer or
thermocouple.
Chapter 5 Thermo 10
Constant Pressure Calorimetry, Problem:
Measuring H 5.44 g of ammonium nitrate was added to 150.0mL of water in a coffee-
cup calorimeter.
This resulted in a decrease in temperature from 18.6 C to 16.2 C.
Because the coffee-cup Calculate the enthalpy change for dissolving NH4NO3(s) in water in
calorimeter. is an kJ/mol.
Assume the solution has a specific heat capacity of 4.18 J/g ? K.
isolated system, What
happens in the coffee cup,
stays in the coffee cup!
No mass loss to the
surroundings.
No heat loss to the
surroundings.

Problem:
5.44 g of ammonium nitrate was added to 150.0mL of water in a coffee-
cup calorimeter.
This resulted in a decrease in temperature from 18.6 C to 16.2 C.
Calculate the enthalpy change for dissolving NH4NO3(s) in water in
kJ/mol.
Assume the solution has a specific heat capacity of 4.18 J/g ? K.
Problem:
5.44 g of ammonium nitrate was added to 150.0mL of water in a coffee-
cup calorimeter.
This resulted in a decrease in temperature from 18.6 C to 16.2 C.
Calculate the enthalpy change for dissolving NH4NO3(s) in water in
kJ/mol.
Assume the solution has a specific heat capacity of 4.18 J/g ? K.

Data Information: Mass of

qsolution
reactant, C, water & temperature 1 mol NH4NO3
change. 5.44 g NH4NO3 0.0680 moles NH4NO3
qsolution + qrxn = 0
80.04 g
Step 1: Cals. Moles of Step 3:
NH4NO3 qsolution msolution C T
Eq. gives mole ratios J
(stoichiometry)
qrxn = q(NH4NO3) qsolution 154.4 g 4.18 (16.2 C 18.6 C)
g C
Step 2:
Determine qsolution = Step 4: rH =qrxn/mol NH4NO3 qsolution 1.55 103 J
mCT
Enthalpy per mole of
reactant

Problem: Constant Volume Calorimetry,

5.44 g of ammonium nitrate was added to 150.0mL of water in a coffee-
cup calorimeter.
Measuring U
This resulted in a decrease in temperature from 18.6 C to 16.2 C.
Calculate the enthalpy change for dissolving NH4NO3(s) in water in Under conditions of
kJ/mol.
Assume the solution has a specific heat capacity of 4.18 J/g ? K. constant volume, any
heat transferred is equal
qsolution = -4.55 103 J to a change of internal
qrxn + qsolution = 0 energy rU.
qrxn = -qsolution = +1.55 103 J

DrH =
qrxn
=
+1.55 103 J

1kJ
= +22.8
kJ qV = rU
moles of reaction 0.0680 moles NH4NO3 103 J mol

The sign is positive indicating an endothermic process.

Chapter 5 Thermo
Constant Volume Calorimetry,
Measuring U
Heats of combustion
(rUocombustion ) are measured
using a device called a Bomb
Calorimeter.
A combustible sample is
reacted with excess O2
The heat capacity of the
bomb is constant.
The heat of reaction is found
by:
qrxn = -Ccal DT
Ccal = Cwater + Cbomb
11
Calculating Heat in an Exothermic
Reaction
Octane, the primary component of gasoline combusts by the
reaction:
C8H18(l) + 25/2 O2(g) 8 CO2(g) + 9H2O(l)
A 1.00 g sample of octane is burned in a bomb calorimeter that
contains 1.20 kg of water surrounding the bomb.
The temperature of the water rises to 33.20 C from 25.00 C
when the octane is reacted.
If the heat capacity of the bomb is 837 J/C, calculate the heat of
reaction per mole of octane.
Since the temperature of the water rose, the reaction must
have been exothermic:
Therefore one can write:
qrxn = qwater + qbomb

Calculating Heat in an Exothermic

Reaction
Hesss Law
qrxn = mwaterCwaterTwater + qbombTwater The overall enthalpy change for a reaction is equal to the sum
of the enthalpy changes for the individual steps in the reaction.
4.184J
-qRXN = 1.20 103 g 33.20 25.00 C Intermediate
g C
Reaction so we can write
J
qwater 837 33.20 25.00 C rH1 + rH2 = rH
C

qbomb Reactants Products What if the enthalpy

rH = ? changes through
qRXN = 4803 J or 48.0 kJ
unknown! another path are know?

- 48.0 kJ kJ The sum of the Hs in one direction must equal the sum
Heat transferred per mole qV: = -5.48 103 in the other direction. Why?
mol mol
1.00g
114.2g Because enthalpy is a state function Path independent!

Hesss law & Energy Level Hesss Law Problem:

Diagrams Example: Determine the rH for the reaction:
3H2(g) + N2(g) 2NH3(g) rHo = ???
Forming CO2 can Given: (1) 2 H2(g) + N2(g) N2H4(g) rH1 = +95.4 kJ
occur in a single (2) N2H4(g) + H2(g) 2NH3(g) rH2 = 187.6 kJ

step or in a two
steps.
rHtotal is the same
no matter which
path is followed.
Notice that the path from reactants to products in the
desired reaction goes through an intermediate
compound in the given reactions.
This means that the path for hydrogen and nitrogen to
produce ammonia goes through hydrazine (N2H4).
Therefore, the path to the enthalpy of the reaction
must be a sum of the two given reactions!
Chapter 5 Thermo 12

Hesss Law Problem: Hesss Law Problem:

Example: Determine the rH for the reaction: Example: Determine the rH for the reaction:
3H2(g) + N2(g) 2NH3(g) rHo = ??? 3H2(g) + N2(g) 2NH3(g) rHo = ???
Given: (1) 2 H2(g) + N2(g) N2H4(g) rH1 = +95.4 kJ Given: (1) 2 H2(g) + N2(g) N2H4(g) rH1 = +95.4 kJ
(2) N2H4(g) + H2(g) 2NH3(g) rH2 = 187.6 kJ (2) N2H4(g) + H2(g) 2NH3(g) rH2 = 187.6 kJ

adding equations (1) & (2) yields: adding equations (1) & (2) yields: Look what happens

2 H2(g) + N2(g)+ N2H4(g) + H2(g) N2H4(g) + 2NH3(g) 2 H2(g) + N2(g)+ N2H4(g) + H2(g) N2H4(g) + 2NH3(g)
/ /
3H2(g) + N2(g) 2NH3(g)

Hesss Law Problem: intermediates

Example: Determine the rH for the reaction: H2(g) +
N2H4(g)
3H2(g) + N2(g) 2NH3(g) rHo = ??? (Step 1) (Step 2)
Given: (1) 2 H2(g) + N2(g) N2H4(g) rH1 = +95.4 kJ Ho = 95.4kJ Ho = 187.6kJ

(2) N2H4(g) + H2(g) 2NH3(g) rH2 = 187.6 kJ reactants

3H2(g) +
N2(g) (Overall)
Ho = 92.2kJ
adding equations (1) & (2) yields: Look what happens
products
2 H2(g) + N2(g)+ N2H4(g) + H2(g) N2H4(g) + 2NH3(g)
/ / 2N3 (g)

3H2(g) + N2(g) 2NH3(g) Reaction (1) is endothermic by 95.4 kJ

therefore
Reaction (2) is exothermic by 187.6 kJ
rH = rH+ +95.4 kJ + (187.6 kJ) = 92.2 kJ
1 rH2 =
Since the exothermicity has a greater magnitude
than the endothermicity, the overall process is
exothermic (rH < 0).

Standard Enthalpies of Formation Enthalpy Values

When 1 mole of compound is formed from its elements, the Since Enthalpy is a state function, enthalpy values
enthalpy change for the reaction is called the enthalpy of depend on the reaction conditions in terms of the
formation, fHo (kJ/mol). phases of reactants and products.
These enthalpies are always reported at Standard
conditions:
1 atm and 25 C (298 K). H2(g) + O2(g) H2O(g) rH = -242 kJ
The standard enthalpies of formation of the most stable form
of any element is zero:
H2(g) + O2(g) H2O(liq) rH = -286 kJ
fH (element) = 0

fH O2(g) = 0 fH O(g) 0 Same reaction, different phases, different enthalpies.

elemental form NOT the elemental form
Chapter 5 Thermo 13

Formation Reactions Question:

What is the formation reaction for potassium
A chemical reaction that describes the formation of permanganate?
one mole of a compound from its elements at
standard state conditions is known as a formation
elements compound
reaction.
K (s) + Mn(s) + 2 O2(g) KMnO4 (s)
The formation of water is given by the reaction:
H2(g) + O2(g) H2O(l) salts are solids at standard state conditions.
Each element and the compound are represented by metals are solids at standard state conditions.
the physical state they take on at 25.0 C and 1 atm oxygen is a gas at standard state conditions.
pressure. (Standard State conditions) balance for one mole of the product

standard state conditions = 25oC and 1 atm

Enthalpy Changes for a Reaction: Consider the Combustion of

Using Standard Enthalpy Values Propane
All components of a reaction can be related back
to their original elements. 3C(s) + 8H2(g)+ 5O2(g)
Each compound has an enthalpy of formation
associated with it. C3H8(g) + 5O2(g) 3CO2(g) + 4 H2O(l)
Reactants require energy to return to component
In order to make CO2(g) and H2O(l) one must break
elements. the propane up into its elements.
Products release energy when formed form This takes energy.
component elements. The elements carbon, hydrogen and oxygen then
Since enthalpy is a state function, the sum of the combine to make the new compounds, CO2 and
above must relate somehow to the overall H2O.
enthalpy of a reaction. This process releases energy.

Enthalpy Changes for a Reaction:

Problem:
Using Standard Enthalpy Values Calculate the rH for CaCO3(s) given the following fH
The sum of the fH for the products multiplied by
the respective coefficients, subtracted by the sum of CaO(s) + CO2(g) CaCO3(s)
the fH for the reactants multiplied by the fH [CaO(s)] = 635.5 kJ/mol
respective coefficients, yields the fH for the
reaction. fH [CO2(g)] = 393.5 kJ/mol
fH [CaCO3(s)] = 1207 kJ/mol

In other words: Energy gained Energy spent = Net Energy

DrH = nD f H (products ) - mD f H (reactants )

n and m are the stoichiometric balancing coefficients.

Chapter 5 Thermo 14

Problem: Problem:
Calculate the rH for CaCO3(s) given the following fH Calculate the rH for CaCO3(s) given the following fH

CaO(s) + CO2(g) CaCO3(s) CaO(s) + CO2(g) CaCO3(s)

fH [CaO(s)] = 635.5 kJ/mol fH [CaO(s)] = 635.5 kJ/mol

DrH = nD f H (products )
fH [CO2(g)] = 393.5 kJ/mol
mD fH (reactants )
DrH = nD f H (products )
fH [CO2(g)] = 393.5 kJ/mol
mD H (reactants )
f

fH [CaCO3(s)] = 1207 kJ/mol fH [CaCO3(s)] = 1207 kJ/mol

1mol CaCO3 1mol CaO 1mol CO2

rH = 1207 kJ/mol (635.5 kJ/mol393.5 kJ/mol)

rH = 178 kJ/mol

Problem: Problem:
The combustionH for naphthalene, C10H8(l) is 5156 kJ/mol. The combustionH for naphthalene, C10H8(l) is 5156 kJ/mol.
Calculate the fH for naphthalene given the following Calculate the fH for naphthalene given the following
enthalpies of formation: enthalpies of formation:
fH [CO2(g)] = 393.5 kJ/mol fH [CO2(g)] = 393.5 kJ/mol

fH [H2O(l)] = 285.7 kJ/mol fH [H2O(l)] = 285.7 kJ/mol

Step 1: Write the balanced equation for the reaction

C10H8(l) + 12 O2(g) 10CO2(g) + 4H2O(l)

Problem:
The combustionH for naphthalene, C10H8(l) is 5156 kJ/mol.
Next recall that:
Calculate the fH for naphthalene given the following
enthalpies of formation:
DrH = nD f H (products ) - mD f H (reactants )
fH [CO2(g)] = 393.5 kJ/mol

C10H8(l) + 12 O2(g) 10CO2(g) + 4H2O(l) fH [H2O(l)] = 285.7 kJ/mol

combustionH 10
= fH [CO2(g)]+ 4 fH [H2O(l)]
fH [C10H8(l)] 10 fH + 4 fH
= [CO2(g)] [H2O(l)]
{fH [C8H10(l)]+ 12 fH [O2(g)]} + 12 fH
{combH [O2(g)]}
From the problem, all quantities are know but f H C10H8 elements = 0
Chapter 5 Thermo 15

Problem:
The combustionH for naphthalene, C10H8(l) is 5156 kJ/mol.
Calculate the fH for naphthalene given the following
enthalpies of formation:
fH [CO2(g)] = 393.5 kJ/mol

fH [H2O(l)] = 285.7 kJ/mol

fH [C10H8(l)] 10 fH + 4 fH
= [CO2(g)] [H2O(l)]
+ 12 fH
{combH [O2(g)]}
H f [C10H8(l)] = elements = 0
10 (393.5 kJ/mol
+ 4 (285.7 kJ/mol) ( 5156 kJ/mol)
= + 79 kJ/mol