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03 Chapter 2 Part 2 Thermochemistry

Thermochemistry is the study of heat changes in chemical reactions. The first law of thermodynamics states that energy cannot be created or destroyed, only transferred or changed in form. Enthalpy (H) is a state function that can be used to calculate the heat of a reaction under constant pressure. The standard enthalpy of formation (ΔfH°) of a compound is the enthalpy change when one mole of the compound is formed from its elements in their standard states. Using ΔfH° values, the standard enthalpy of reaction (ΔrH°) can be calculated to determine if a reaction is exothermic or endothermic.

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0% found this document useful (0 votes)
37 views58 pages

03 Chapter 2 Part 2 Thermochemistry

Thermochemistry is the study of heat changes in chemical reactions. The first law of thermodynamics states that energy cannot be created or destroyed, only transferred or changed in form. Enthalpy (H) is a state function that can be used to calculate the heat of a reaction under constant pressure. The standard enthalpy of formation (ΔfH°) of a compound is the enthalpy change when one mole of the compound is formed from its elements in their standard states. Using ΔfH° values, the standard enthalpy of reaction (ΔrH°) can be calculated to determine if a reaction is exothermic or endothermic.

Uploaded by

Ako si Gian
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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Chapter 2, Part 2.

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

System Wall Allows flow of


Matter? Energy?
Permeable,
diathermal
Impermeable,
diathermal
Impermeable,
adiabatic
Introduction to Thermodynamics

A thermodynamic process is defined as the transformation of a thermodynamic


system undergoes changes from one system to another. They can be classified as
flow or nonflow and reversible and irreversible processes.

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

Thermodynamics is the scientific study of energy conversion


from one form to another

The First Law of Thermodynamics states that energy can be


converted from one form to another but cannot be created or
destroyed.
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

A more useful form of the first law is


ΔUsys = 𝑞 + 𝑤
The First Law of Thermodynamics

Internal energy is the total energy of a system at equilibrium.


Heat and Work

The sign conventions for q and w are as follows:

Work done by the system on the surroundings -


Work done by the surroundings on the system +
Heat absorbed by the system from the surroundings (endothermic process) +
Heat released by the system to the surroundings (exothermic process) -
The First Law of Thermodynamics

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.

thus, the sum of the energy change must be zero

This is the concept of first law of thermodynamics.


The First Law of Thermodynamics

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.

Work is the transfer of energy accomplished by a force moving a mass some


distance against resistance

One way to illustrate work is by expansion or compression of a gas in a piston


Heat and Work

Pressure- Volume work


Expansion – gas is doing work

P1> Pext P2= Pext


Heat and Work

Pressure- Volume work


Compression – surroundings does work

Pext> P1 P2= Pext


Heat and Work

• Isothermal Process – undergoes changes under a constant temperature

• Isobaric Process – undergoes changes under a constant pressure

• Isochoric Process – undergoes changes under constant volume

• 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

(b) against a constant pressure of 4.00 atm.


Heat and Work

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

To apply the first law of thermodynamics, consider a common laboratory situations:


one in which the volume is kept constant, and the other in which the pressure
applied on the system is kept constant. Recall equation

At constant volume

At constant pressure
Enthalpy of Chemical Reactions

Enthalpy , on the other hand, is another thermodynamic function of a system


defined by the equation

Derivation of enthalpy 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:

If the change in enthalpy is negative, then it the chemical reaction underwent an


exothermic process. Otherwise, if the change in enthalpy is positive, then it
underwent an endothermic process.
Enthalpy of Chemical Reactions

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:

1. Always specify the physical states of all reactants and products.


2. If multiplying both sides of a thermochemical equation by a factor n, the must
also change by the same factor
3. Writing the reverse equation would make the sign of reversed.
Enthalpy of Chemical Reactions

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

Substances are said to be at standard state at one atmosphere pressure. By


convention, the standard enthalpy of formation of any element in its most stable
form is zero.

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

where , , , and are stoichiometric coefficients. The is given by


Standard Enthalpy of Formation and 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

We can write the as

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

Many compounds cannot be directly synthesized from their elements, especially


when reactions proceeds too slowly or there are other side reactions in a chemical
reaction.

In these cases, can be determined by an indirect approach based on Hess’s Law,


which states that When the reactants are converted into products, the change in
enthalpy is the same whether the reaction takes place in one step or in a series of
steps.
Standard Enthalpy of Formation and Reaction

Find the of for the reaction


Given
Standard Enthalpy of Formation and Reaction

Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements

Given the equations for each steps


Standard Enthalpy of Formation and Reaction

Calculate the standard enthalpy of formation of carbon disulfide (CS 2) from its elements,
given that
Standard Enthalpy of Formation and Reaction

The thermite reaction involves aluminum and iron(III) oxide

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

Calculate the change in internal energy when 2 moles of CO are converted to 2


moles of CO2 at 1 atm and 25°C
Comparison of and

What is the for the formation of 1 mol of at 1 atm and 25°C?


Comparison of and

Which of the constant-pressure processes shown here has the smallest difference
between and ? Why?

A. Water to water vapor

B. Water to ice

C. Ice to water vapor


Calorimetry

Heat changes involved in physical or chemical processes are measured with a


calorimeter. Calorimetry is the measurement of heat changes involved in any
processes.
Calorimetry

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 quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling substance used in moth repellents,


was burned in a constant-volume bomb calorimeter. Consequently, the temperature of the water
rose from 20.28°C to 25.95°C. If the heat capacity of the bomb plus water was 10.17 kJ/°C, calculate
the heat of combustion of naphthalene on a molar basis; that is, find the molar heat of combustion.
Calorimetry: Constant-Volume Calorimetry

A quantity of 1.922 g of methanol (CH3OH) was burned in a constant-volume bomb calorimeter.


Consequently, the temperature of the water rose by 4.20°C. If the heat capacity of the bomb plus
water was 10.4 kJ/°C, calculate the molar heat of combustion of methanol.
Calorimetry: Constant-Pressure Calorimetry
Calorimetry: Constant-Pressure 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.

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