03 Chapter 2 Part 2 Thermochemistry
03 Chapter 2 Part 2 Thermochemistry
Thermochemistry
Chapter Outline
• Introduction to Thermodynamics
• The First Law of Thermodynamics
• Heat and Work
• Enthalpy of Chemical Reactions
• Standard Enthalpy of Formation and Reaction
• Comparison of and
• Calorimetry
Introduction to Thermodynamics
Thermochemistry
The study of heat changes in chemical reactions.
Chemical reactions absorb or produce (release) energy, generally in the form of
heat.
Heat is the transfer of thermal energy between two bodies that are at different
temperatures. Spontaneously, heat flows from the region possessing high thermal
energy to low thermal energy.
Introduction to Thermodynamics
Thermochemistry
The study of heat changes in chemical reactions.
Chemical reactions absorb or produce (release) energy, generally in the form of
heat.
Heat is the transfer of thermal energy between two bodies that are at different
temperatures. Spontaneously, heat flows from the region possessing high thermal
energy to low thermal energy.
Introduction to Thermodynamics
Chemical reactions take place in a specific place called the system, with the
surroundings around it.
Introduction to Thermodynamics
Types of Wall
1. Rigid ____________________
2. Nonrigid ____________________
3. Permeable ____________________
4. Impermeable ____________________
5. Adiabatic ____________________
6. Diathermal ____________________
Introduction to Thermodynamics
Types of System
An irreversible process is one in which the system and the surrounding cannot go
back to their original states after undergoing thermodynamic changes.
A reversible process is one which the energy change in every step of the process
can be reversed in direction by an infinitesimal change in any of the variables acting
on the system.
Introduction to Thermodynamics
Properties of Systems
Extensive properties are properties that are dependent on the amount of matter
present. Some examples include volume, number of moles, internal energy, and
entropy.
Intensive properties are properties that are independent on the amount of matter
present. Some examples include temperature, pressure, and density.
Introduction to Thermodynamics
States of system
The state of a system is the values of all relevant macroscopic properties, like
composition, energy, temperature, pressure, and volume.
State functions are values/properties that are determined by the state of the
system, regardless of how the condition was achieved.
Path Functions are values/properties that depend on the process to get into
another state.
The First Law of Thermodynamics
Internal Energy (E): total energy of a system at equilibrium. Comes from the total
kinetic energy and potential energy of the system
The changes in internal energy also is the difference of the internal energy of the
final state from its initial state, that is
Whatever changes in the internal energy of the system is, that has to be transferred
to the surroundings.
Calculate the change in internal energy for a process in which the system absorbs
150 J of heat from the surroundings and does 95 J of work on the surroundings.
The First Law of Thermodynamics
A system releases 67.5 kJ of heat to its surroundings while the surroundings do 54.0 kJ
of work on the system. Calculate ΔU and determine whether the process is endothermic
or exothermic.
Heat and Work
Heat is the transfer of thermal energy between two bodies that are at different
temperatures.
• Adiabatic Process – changes in a temperature in a system occur but there is no heat flow
exchanged between the system and surroundings
Heat and Work
A gas expands from 264 mL to 971 mL. Calculate the work done (in joules) by the gas if it
expands
(a) against a vacuum and
A 4.00 L sample of H2 at 15.0 atm and 25°C is allowed to expand to a final pressure
of 1.00 atm. Calculate the work involved if the gas expands isothermally
Enthalpy of Chemical Reactions
At constant volume
At constant pressure
Enthalpy of Chemical Reactions
For any reactions, the change in enthalpy is called the enthalpy of reaction, which is
the difference between the enthalpies of the products and the enthalpies of the
reactants:
Enthalpy changes in a chemical reaction can be paired with the mass relationships
that took place. For example, the combustion of methane gas is accompanied by a
release of 890.4 kJ of energy. This can be represented by a thermochemical
equation
Enthalpy of Chemical Reactions
It is essential that an equation must be balanced. Also, the following guidelines are
used to interpret thermochemical equations:
Calculate the heat evolved when 87.9 g of SO2 (64.07 g/mol) is converted to SO3.
Enthalpy of Chemical Reactions
Calculate the heat evolved when 266 g of white phosphorus (P4) burns in air
according to the equation
Standard Enthalpy of Formation and Reaction
The enthalpy change can be determined if the actual enthalpies of the reactants or
products is known. However, there is no way to measure the absolute value of
enthalpy of a given substance. To resolve this, we obtain their relative values to an
arbitrary reference.
This reference point for all enthalpy expressions is called the standard enthalpy of
formation .
Standard Enthalpy of Formation and Reaction
Based on this reference, we can now define that the standard enthalpy of formation
of a compound as the heat change that results when one mole of the compound is
formed from its elements at a pressure of one atmosphere.
Standard Enthalpy of Formation and Reaction
Since the standard enthalpies of formation is now known, the standard enthalpy or
reaction (), the enthalpy of a reaction carried out at one atmosphere, can now be
calculated. For example, consider the hypothetical reaction
However, to calculate , we have to establish the values for of the reacting species
by applying direct or indirect methods.
Direct Method
Direct method of determining the enthalpy of formation involves reactions that go
into completion. For example
Standard Enthalpy of Formation and Reaction
Since the enthalpy of formation of carbon as graphite and oxygen is zero, therefore,
Standard Enthalpy of Formation and Reaction
Standard Enthalpy of Formation and Reaction
Standard Enthalpy of Formation and Reaction
Indirect Method
Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements
Calculate the standard enthalpy of formation of carbon disulfide (CS 2) from its elements,
given that
Standard Enthalpy of Formation and Reaction
This reaction is highly exothermic, and the liquid iron formed is used to weld metals.
Calculate the heat released in kilojoules per gram of Al reacted with Fe 2O3. The for Fe(l) is
12.40 kJ/mol and for Fe2O3 is -822.2 kJ/mol. The molar mass of Al is 26.98g.
Standard Enthalpy of Formation and Reaction
Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. Calculate
the heat released (in kilojoules) per gram of the compound reacted with oxygen. The
standard enthalpy of formation of benzene is 49.04 kJ/mol
Comparison of and
Enthalpy and internal energies are both energies involving heat involved in a
reaction. However, internal energy do also include work in its equation. To derive a
general equation relating these two energies will give us
Comparison of and
Which of the constant-pressure processes shown here has the smallest difference
between and ? Why?
B. Water to ice
A 466-g sample of water is heated from 8.50°C to 74.60°C. Calculate the amount of
heat absorbed (in kilojoules) by the water. (c = 4.184 J/g°C)
Calorimetry
An iron bar of mass 869 g cools from 94°C to 5°C. Calculate the heat released (in
kilojoules) by the metal. (c = 0.444 J/g°C)
Calorimetry
Types of Calorimetry
• Constant-Volume Calorimetry / Bomb Calorimeter
• Constant-Pressure Calorimetry
Calorimetry: Constant-Volume Calorimetry
Calorimetry: Constant-Volume Calorimetry
A lead (Pb) pellet having a mass of 26.47 g at 89.98°C was placed in a constant-pressure calorimeter
of negligible heat capacity containing 100.0 mL of water. The water temperature rose from 22.50°C
to 23.17°C. What is the specific heat of the lead pellet?
Calorimetry: Constant-Pressure Calorimetry
A quantity of 100 mL of 0.500 M HCl was mixed with 100 mL of 0.500 M NaOH in a constant-
pressure calorimeter of negligible heat capacity. The initial temperature of the HCl and NaOH
solutions was the same, 22.50°C, and the final temperature of the mixed solution was 25.86°C.
Calculate the heat change for the neutralization reaction on a molar basis.