THERMOCHEMISTRY

Module II
 01
FORMS OF ENERGY & ITS
INTERCONVERSION
LESSONS
02 ENTHALPY

03 CALORIMETRY

04
STOICHIOMETRY OF THERMOCHEMICAL
EQUATIONS
WHAT IS
THERMOCHEMISTRY?
Thermochemistry is the
branch of thermodynamics
that deals with heat in
chemical and
physical change.
Forms of Energy and
Its Interconversion
WHAT IS ENERGY?

Energy is the capacity to

supply heat or do work.
Types of Energy
➢ Potential energy
➢ Kinetic energy

Potential energy is converted to kinetic

energy, which appears as work and
heat.
Potential
Energy (PE) When objects that
attract are moved
An object has PE apart, PE increases.
when it Similarly, when
experiences objects that repel are
attractions or pushed together, PE
repulsions toward increases.
other objects.
 An object has KE if it is
Kinetic moving.
Energy
(KE)
Defining the System
and Surrounding
➢ System is the part of the universe
we are focusing.
➢ Surrounding is everything around
the system.
Types of Systems in
Thermodynamics
➢ An open system can exchange
both energy and matter with its
surroundings.
Types of Systems in
Thermodynamics
➢ A closed system can exchange
only energy with its
surroundings, not matter.
Types of Systems in
Thermodynamics
➢ An isolated system is one that cannot
exchange either matter or energy with its
surroundings.
➢ Processes that occur within an isolated
system are called adiabatic.
Energy Change (ΔE): Energy
Transfer to or from the System
Internal Energy, E, is the sum of the
potential energy and kinetic energy
that each particle in a system has.
 ΔE = E - E
final initial

ΔE = E
products -E
reactants
Two (2) Ways a System can
change its Internal Energy
➢ By releasing some energy in a
transfer to the surroundings
Efinal < Einitial so ΔE < 0
Two (2) Ways a System can
change its Internal Energy
➢ By absorbing some energy in a
transfer from the surroundings
Efinal > Einitial so ΔE > 0
Forms of Energy Transfer
➢ Heat
➢ Work
Heat, q
or thermal energy is the energy
transferred as a result of a difference in
temperature between the system and
the surroundings.
Work, w
➢ the energy transferred when
an object is moved by a force.
Energy diagrams for the transfer of internal energy (E)
between two systems and their surroundings.
 ΔE = q + w
The values of q and w (and,
therefore, of ΔE) can have
either a positive or negative
sign.
We define the sign of the energy change
from the system’s perspective:
• Energy transferred into the system is
positive because the system ends up with
more energy.

• Energy transferred out from the system is

negative, because the system ends up
with less energy.
Energy ● Where w = 0,
Transferred as
Heat Only

ΔE = q + 0 = q
 ● Heat flowing out
Energy from a system
Transferred as
Heat Only
● Heat flowing into a
system
 Heat flowing out from a system

System releases energy as heat ⟶ q is

negative ⟶ Efinal < Einitial ⟶ ΔE is negative
Heat flowing into a system

System absorbs energy as heat ⟶

q is positive ⟶ Efinal > Einitial ⟶ ΔE
is positive
Energy ● Where q = 0,
Transferred as
Work Only

ΔE = 0 + w = w
 ● Work done by a
Energy system
Transferred as
Work Only
● Work done on a
system
Work done by a system

System releases energy as work

done by it ⟶ w is negative ⟶ Efinal
< Einitial ⟶ ΔE is negative
Work done on a system

System absorbs energy as work

done on it ⟶ w is positive ⟶ Efinal
> Einitial ⟶ ΔE is positive
The Sign Conventions* for q, w, and ΔE
 Law of Conservation of
Energy: The total energy of
the universe is constant.
The First Law of
Thermodynamics

ΔEuniverse = ΔEsystem + ΔEsurroundings = 0

 The SI unit of energy is the
Joule (J). It is the unit for
work.
Units of Energy

1 Joule (J) = 1kg∙m2/s2

 Calorie (cal) is the quantity
of energy needed to raise
the temperature of 1 g of
water by 1°C.
Units of Energy
1 cal = 4.184 J
1 J = 0.2390 cal
1 kJ = 1000 J = 0.2390 kcal =
239.0 cal
1 kcal = 1000 cal = 4184 J
 British thermal unit (Btu) is
the quantity of energy
required to raise the
temperature of 1 lb of water
by 1°F
Units of Energy

1 Btu = 1055 J
Sample
Problem 1
Sample Problems
Sample Problem 1

1) When gasoline burns in a car engine, the heat

released causes the gaseous products CO2 and H2O to
expand, which pushes the pistons outward. Excess
heat is removed by the radiator. If the expanding
gases do 451 J of work on the pistons and the system
releases 325 J to the surroundings as heat, calculate
the change in energy (ΔE) in J, kJ, and kcal.
Sample Problem 2

1) A sample of liquid absorbs 13.5

kJ of heat and does 1.8 kJ of
work when it vaporizes.
Calculate ΔE (in J).
Sample Problem 3

1) In a reaction, gaseous reactants form a

liquid product. The heat absorbed by
the surroundings is 26.0 kcal, and the
work done on the system is 15.0 Btu.
Calculate ΔE (in kJ).
 State Functions and the Path Independence
of the Energy Change

● The internal energy (E) of a system is called a

state function, a property dependent only on
the current state of the system (its
composition, volume, pressure, and
temperature), not on the path the system
takes to reach that state.
 Calculating ● Mechanical work
Pressure- ➢ the work done when the
Volume Work volume of the system
(PV Work) changes in the presence of
an external pressure, P
 Calculating W = -PΔV
Pressure-
Volume Work
(PV Work) Where ΔV = Vfinal – Vinitial
The volume of Work of Expansion
the system may
➢

The volume of a gaseous system will

increase increase if the temperature is raised
(expand) or (Charles’s law) or if a chemical reaction
decrease results in a net increase in
(contract)
the number of moles of gas (Avogadro’s
law)
Example
combustion of propane:
C3H8(g) + 5O2(g) ⟶ 3CO2(g) + 4H2O(g)
6 (1 + 5) mol of gas 7 (3 + 4) mol of gas

Vfinal > Vinitial; ΔE = (−)

 ➢ Work of Contraction
The volume of
the system may A gaseous system will
increase decrease in volume if the
(expand) or temperature is lowered or if a
decrease reaction results in a net
(contract) decrease in the number of
moles of
gas,
Example
production of ammonia:
3H2(g ) + N2(g) ⟶ 2NH3(g)
4 (3 + 1) mol of gas 2 mol of gas

Vfinal < Vinitial; ΔE = (+)

Sample
Problem 1
Sample Problems
Sample Problem 1
1) A reaction taking place in a container with a
piston-cylinder assembly at constant
temperature produces a gas, and the volume
increases from 125 mL to 652 mL against an
external pressure of 988 torr. Calculate the
work done (in J; 1 atm·L = 101.3 J).
Sample Problem 2

1) A gas is compressed at constant

temperature from a volume of 5.68 L
to a volume of 2.35 L by an external
pressure of 732 torr. Calculate the
work done (in J).
Sample Problem 3

1) A gas-producing reaction occurs in a

container with a piston-cylinder assembly
under an external pressure of 5.5 atm. At
constant temperature, the volume
increases from 10.5 L to 16.3 L. Calculate
the work done (in J).
Enthalpy
WHAT IS ENTHALPY? Enthalpy is the sum of the
internal energy and the
product of the pressure
and volume of a
thermodynamic system. It
is also a state function.
The ΔH = ΔE + PΔV
Meaning of The change in enthalpy is the
Enthalpy change in the system’s internal
H = E + PV energy plus the product of the
pressure, which is constant,
and the change in volume (ΔV)

ΔH = ΔE + PΔV = qP
At constant pressure, the change in enthalpy (ΔH) equals
the heat absorbed or released
 Knowing the enthalpy
change of a system tells us
Comparing ΔE and ΔH a lot about its energy
change as well. In fact,
because many reactions
involve little (if any) PV
work, most (or all) of the
energy change is due to a
transfer of heat.
3 CASES
 ΔH = H final − H initial = H products − H reactants

❖ The sign of ΔH indicates whether heat is

absorbed or released during the reaction.
❖ The sign of ΔH by imagining the heat as a
“reactant” or a “product.”
 Exothermic and
Endothermic Processes
An exothermic process releases
heat and results in a decrease in
the enthalpy of the system:

Exothermic: Hproducts < Hreactants

so ΔH < 0
Exothermic process

● CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(g) + heat

 Exothermic and
Endothermic Processes
An endothermic process absorbs
heat and results in an increase in
the enthalpy of the system:

Exothermic: Hproducts > Hreactants

so ΔH > 0
Endothermic process

● Heat + H2O(g) ⟶ H2O(ℓ)

Calorimetry: Measuring the Heat of
a Chemical or Physical Change
 The quantity of heat (q)
absorbed or released by
an object is proportional
Specific Heat to its temperature change
Capacity

q
q α ΔT or q = constant x ΔT or ---- = constant
ΔT
 ● Heat capacity is the quantity of
heat required to change its
temperature by 1 K

Heat Capacity, C
q
Heat capacity (C) = ---- (in units of J/K or J/°C)
ΔT
Specific Heat Capacity, c
Specific heat capacity is the quantity of heat
required to change the temperature of 1 gram
of substance or material by 1 K.
Specific heat capacity, c
q
Specific heat capacity (c) = -------------- (in units of J/g∙K or J/g∙°C)
mass x ΔT

q = c x mass x ΔT
Sample
Problem 1
Sample Problems
Sample Problem 1

A layer of copper welded to the bottom of

a skillet weighs 125 g. How much heat is
needed to raise the temperature of the
copper layer from 25°C to 300.°C? The
specific heat capacity (c) of Cu is 0.385
J/g•°C).
Sample Problem 2

Before baking a pie, you line the bottom of

an oven with a 7.65-g piece of aluminum
foil and then raise the oven temperature
from 18°C to 375°C. The specific heat
capacity (c) of Al is 0.890 J/g•°C).
Calculate the heat absorbed by the
aluminum foil.
 ● It is when the mass of the
substance is equal to its molar
mass.
Heat capacity is the quantity of
Molar Heat
●

heat required to change the T of 1

Capacity, Cm mole of a substance by 1°C.
Molar heat q
capacity (Cm) = ---------------------------
amount (mol) x ΔT
Calorimeter

● Measures the heat released (or absorbed)

during a process either at constant P (qp =
ΔH) or at a constant volume (qv = ΔE).
 ● Constant-Pressure
calorimetry – carried out in
a coffee cup calorimeter
Two Major
Types of
Calorimetry
● Constant-Volume
calorimetry – carried out in
a bomb calorimeter
Coffee cup calorimeter Bomb calorimeter
 ● Bomb calorimeter – a device
commonly used to measure the
heat of combustion reactions,
Constant-
usually involving fuels or foods
Volume
Calorimetry qcalorimeter = Ccalorimeter x Δtcalorimeter
-qrxn = qcalorimeter;
ΔE = q + w = qv + 0 = qv
Sample
Problem 1
Sample Problems
Sample Problem 1
Oxyacetylene torches produce such high
temperatures that they are often used to weld
and cut metal. When 2.50 g of acetylene (C2H2) is
burned in a bomb calorimeter with a heat
capacity of 10.85 kJ/°C, the temperature increases
from 23.488°C to 34.988°C. What is ΔE (in
kJ/mol) for this combustion reaction?
 Solution

Find ΔT.
Step 1

Step 2 Calculate the heat absorbed by the

calorimeter.

Step 3 Calculate ΔE
Sample Problem 2

A chemist burns 0.8650 g of graphite in a bomb

calorimeter, and CO2 forms. If 393. 5 kJ of heat
is released per mole of graphite and ΔT is
3.116 K, what is the heat capacity of the bomb
calorimeter?
Sample Problem 3
A manufacturer claims that its new dietetic dessert
has “fewer than 10 calories per serving.” To test
the claim, a chemist at the Department of
Consumer Affairs places one serving in a bomb
calorimeter and burns it in O2. The initial
temperature is 21.862°C, and the temperature rises
to 26.799°C. If the heat capacity of the calorimeter
is 8.151 kJ/°C, is the manufacturer’s claim correct?
Hess’s Law: Finding of Any Reaction
 ● states that the enthalpy change
of an overall process is the sum
of the enthalpy changes of its
individual steps.
Hess’s Law

ΔHoverall = ΔH1 + ΔH2 +…. ΔHn

 Rules of Thermohemistry

Rule 1 Rule 2 The value of ΔH

for a reaction is
The magnitude of ΔH for a reaction
the same
ΔH is directly is equal in
whether it
proportional to magnitude but
occurs in one
the amount of opposite in sign
step or in a
reactant or to ΔH for the
series of steps.
product. reverse
(Hess’s Law)
reaction.

Rule 3
Sample
Problem 1
Sample Problems
Sample Problem 1
Carbon monoxide, CO, is a poisonous gas. It can be
obtained by burning carbon in a limited amount of
oxygen. Given

(1) C(g) + O₂(g) → CO₂ ΔH = − 393.5 kJ

(2) 2CO(g) + O₂(g) → 2CO₂ ΔH = − 566.0 kJ

Calculate the ΔH for the reaction

C(s) + ½O₂(g) → CO(g) ΔH = ?
 Sample Problem 2
Two pollutants that form in automobile exhaust are CO and NO.
An environmental chemist must convert these pollutants to less
harmful gases through the following:
CO(g) + NO(g) → CO₂(g) + ½N₂(g) ΔH = ?

Given the ff. information, calculate the unknown ΔH:

Eqn. 1 CO(g) + ½O₂(g) → CO₂(g) ΔH = − 283 kJ
Eqn. 2 N₂(g) + O₂(g) → 2NO(g) ΔH = 180.6 kJ
Standard Enthalpies of Reaction (ΔH°rxn)
Standard
States
● For a gas, the standard state is 1 atm and ideal behavior
● For a substance in aqueous solution, the standard state is
1 M concentration
● For a pure substance (element or compound), the
standard state is usually the most stable form of the
substance at 1 atm and 25°C
Formation Equation and Their Standard Enthalpy
Changes
Standard Enthalpy of
Formation Equation Formation, ΔH°f

● One (1) mole of ● Aka standard heat of

a compound formation
forms from its ● Is the enthalpy change for
elements. the formation equation
when all the substances
are in their standard states.
Detemining ΔHrxn from ΔH°f values for reactants and
products
Sample
Problem 1
Sample Problems
Sample Problem 1
Nitric acid is used to make many products,
including fertilizers, dyes, and explosives. The first
step in its production is the oxidation of ammonia:

4 NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)

Calculate the ΔH°rxn from ΔH°f values.

Sample Problem 2
Tetraphosphorus decoxide reacts vigorously with
water to form phosphoric acid, one of the top-10
industrial chemicals:

P4O10(s) + 6H2O(l) → 4H3PO4(l)

Calculate the ΔH°rxn from ΔH°f values.

Sample Problem 3
Use the following to find ΔH°f of methanol, CH3OH(l):

3
CH3OH(l) + O2(g) → CO2(g) + H2O(g) ΔH°rxn = −638.6 kJ
2

ΔH°f of CO2(g) = −393.5 kJ/mol

ΔH°f of H2O(g) = −241.826 kJ/mol
Thank You!