Petrucci 11e PPT Ch07

GENERAL CHEMISTRY
PRINCIPLES AND MODERN APPLICATIONS

ELEVENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Thermochemistry 7
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
Slide 7 - 1 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

CONTENTS
Thermochemistry 7-1 Getting Started: Some
Terminology
7-2 Heat
7-3 Heats of Reaction
and Calorimetry
7-4 Work
7-5 The First Law of
Thermodynamics
7-6 Application of the First Law to
Chemical and Physical Changes
7-7 Indirect Determination
of DrH: Hess’s Law
7-8 Standard Enthalpies of
Formation
7-9 Fuels as Sources of
Energy
7-10 Spontaneous and Nonspontaneous
Processes: An Introduction

7-1 Getting Started: Some Terminology
FIGURE 7-1
Systems and their surroundings

FIGURE 7-2
Potential energy (P.E.) and kinetic energy (K.E.)

Isolated system

1 J = 1 kg m2 s–2
Kinetic Energy
2
1 kg m
Ek = mu 2
[Ek ] = = J
2 s
Work
w=Fxd
m m
= mxaxd [w ] = kg 2 = J
s
7-2 Heat
Thermal Energy
Kinetic energy associated with random molecular motion.
In general proportional to temperature.
An intensive property.
Heat and Work

q and w.
Energy changes.

Internal energy is transferred between a system and its
surroundings as a result of a temperature difference.
Heat “flows” from hotter to colder.

Temperature may change.
Phase may change (an isothermal process).

calorie (cal)
The quantity of heat required to change the temperature
of one gram of water by one degree Celsius.
Joule (J)
SI unit for heat
1 cal = 4.184 J

Heat Capacity
The quantity of heat required to change the temperature of a
system by one degree.
Heat capacity
∆T = Tf – Ti

Molar heat capacity at constant pressure, cP,m
quantity of heat required to raise the temperature of
one mole of substance by one degree celcius.
Specific heat capacity, cp.

quantity of heat required to raise the temperature of
one gram of substance by one degree celcius.
(7.5)

Law of conservation of energy
In interactions between a system and its

surroundings the total energy remains
constant— energy is neither created nor destroyed.
qsystem + qsurroundings = 0
qsystem = –qsurroundings

Experimental Determination
of Specific Heat Capacities
FIGURE 7-3
Determining the specific heat of lead – Example 7-2 illustrated

7-3 Heats of Reaction and Calorimetry
Chemical energy.
Energy associated with chemical bonds and intermolecular
interactions. Contributes to the internal energy of a system.
Heat of reaction, qrxn.
The quantity of heat exchanged between a system and its
surroundings when a chemical reaction occurs within the system, at
constant temperature.

FIGURE 7-4
Conceptualizing a heat of reaction at constant temperature

Exothermic and endothermic reactions

KEEP IN MIND
that the temperature of a
reaction mixture usually
changes during a reaction, so
the mixture must be returned
to the initial temperature
(actually or hypothetically)
before we assess how much
heat is exchanged with the
surroundings.

A bomb calorimeter assembly
qrxn = –qcal
qcal = q bomb + q water + q wires +…
Define the heat capacity of the

calorimeter:
qcal = ∑mici∆T = Ccal∆T
all i
FIGURE 7-5
A bomb calorimeter assembly

The Coffee-Cup Calorimeter
A simple calorimeter.
Well insulated and therefore
isolated.
Measure temperature change.
qrxn = –qcal
FIGURE 7-6
A Styrofoam “coffee-cup” calorimeter

7-4 Work
In addition to heat effects
chemical reactions may also
do work.
Gas formed pushes against the

atmosphere.
The volume changes.
Pressure-volume work.
FIGURE 7-7
Illustrating work (expansion) during the chemical reaction
2 KClO3(s) 2 KCl(s) + 3 O2(g)
w=Fxd
= –(M x g)×∆h
(M x g)
=– ×∆h ×A
A
= –P∆V
w = –Pext∆V
FIGURE 7-8
Pressure-volume work

7-5 The First Law of Thermodynamics
Internal Energy, U.
Total energy (potential and kinetic) in a
system.
• Translational kinetic energy.

• Molecular rotation.
• Bond vibration.
• Intermolecular attractions.
• Chemical bonds.
• Electrons.
FIGURE 7-9
Some contributions to the internal energy of a system

7-5 The First Law of Thermodynamics
A system contains only internal energy.

A system does not contain heat or work.
These only occur during a change in the system.
∆U = q + w

An isolated system is unable to exchange either heat or
work with its surroundings, so that Uisolated system = 0,
and we can say:
The energy of an isolated system is constant

FIGURE 7-10
Illustration of sign conventions used in thermodynamics

Functions of State
Any property that has a unique value for a specified state of a
system is said to be a
function of state or a state function.
Water at 293.15 K and 100 kPa is in a specified state.
d = 0.99820 g/mL
This density is a unique function of the state.

It does not matter how the state was established.

U is a function of state.
Not easily measured.
∆U has a unique value between

two states.
Is easily measured.

Path Dependent Functions
Changes in heat and work are not functions of state.
Consider process in Example 7.5 and Figure 7-8

w = −1.24 x 102 J in a one step expansion of gas:
let us consider a two step process from

2.40 atm to 1.80 atm, and finally to 1.20 atm.

w = (−1.80 atm)(1.36−1.02)L
– (1.30 atm)(2.04−1.36)L
= −0.61 L atm – 0.82 L

atm = −1.43 L atm
= −1.44 x 102 J
Compared −1.24×102 J for

the one stage process
FIGURE 7-11
A two-step expansion for the gas shown in Figure 7-8

Reversible process
infinitesimal changes
in a system variable
Irreversible process
stepwise processes are
irreversible
FIGURE 7-12
A different method of achieving the expansion of a gas

FIGURE 7-13
Three different paths leading to the same internal energy change in a system

7-6 Application of the First Law to
Chemical and Physical Changes
Reactants → Products
Ui Uf
∆U = Uf −Ui
∆U = qrxn + w
In a system at constant volume (bomb calorimeter):

∆U = qrxn + 0 = qrxn = qv
But we live in a constant pressure world!

How does qp relate to qv?

qV = qP + w
We know that w = –P∆V and ∆U = qv, therefore:
∆U = qP – Pext∆V
Uf–Ui = qP – PextVf+PextVi
(Uf + PextVf)–(Ui+PextVi)= qP
H = U + PV
∆H = Hf – Hi = qP
qP = ∆U + P∆V ∆U = ∆H– P∆V

qV = ∆U = ∆H–P∆V
= –563.5 kJ/mol
w = P∆V = P(Vf – Vi)

= RT(nf – ni)
= –2.5 kJ
qP = ∆H
= –566 kJ/mol
∆H = ∆U + ∆ngasRT
FIGURE 7-14 P q = q + ∆n RT
V gas
Comparing heats of reaction at constant volume and constant pressure for
the reaction 2 CO(g) + 2 O2(g) 2 CO2(g)
Enthalpy of Reaction: r
2 CO (g) + O2 (g) 2 CO2 (g) ΔH = –566 kJ mol–1
per mole of reaction
one mole of reaction refers to the situation in

which the extent of reaction is equal to 1 mol
C12H22O11 (g) + 12 O2 (g) 12 CO2 (g) + 11 H2O (g)
ΔH = –5.65✕103 kJ mol–1

Physical Significance of Enthalpy Change
 represents the heat transferred
under constant-pressure conditions.
No simple physical or molecular interpretation.
r = qp

Enthalpy Change Accompanying
a Change in State of Matter
Molar enthalpy of vaporization:
H2O (l) → H2O(g) ∆H = 44.0 kJ at 298.15 K
Molar enthalpy of fusion:

H2O (s) → H2O(l) ∆H = 6.01 kJ at 273.15 K

Standard States and Standard
Enthalpy Changes
Define a particular state as a standard state.
Standard enthalpy of reaction, ∆Hº

The enthalpy change of a reaction in which all reactants and products are
in their standard states.
Standard State
The pure element or compound at a pressure of 1 bar and at the
temperature of interest.

Enthalpy Diagrams
FIGURE 7-15
Enthalpy Diagrams

7-7 Indirect Determination of ∆H:
Hess’s Law
• ∆H is an extensive property.
Enthalpy change is directly proportional to the amount of
substance in a system.
N2(g) + O2(g) → 2 NO(g) ∆H° = +180.50 kJ mol–1
½N2(g) + ½O2(g) → NO(g) ∆H° = +90.25 kJ mol–1
• ∆H changes sign when a process is reversed
NO(g) → ½N2(g) + ½O2(g) ∆H° = −90.25 kJ mol–1

FIGURE 7-17
An Enthalpy diagram illustrating Hess’s Law

• Hess’s law of constant heat summation
½N2(g) + O2(g) → NO(g) + ½ O2 (g) ∆Hº = +90.25 kJ mol–1

NO(g) + ½O2(g) → NO2(g) ∆Hº = –57.07 kJ mol–1
½N2(g) + O2(g) → NO2(g) ∆Hº = +33.18 kJ mol–1
If a process occurs in stages or steps (even hypothetically), the enthalpy change

for the overall process is the sum of the enthalpy changes for the individual steps

7-8 Standard Enthalpies of Formation
∆Hfº
The enthalpy change that occurs in the formation of one mole
of a substance in the standard state from the reference forms
of the elements in their standard states.
The standard enthalpy of formation is 0 for a pure element in its reference form.

C (graphite) C (diamond) ΔH = 1.9 kJ mol–1
Diamond and graphite

Br2(l) Br2(g)
Hfº = 30.91 kJ
Liquid bromine vaporizing

FIGURE 7-18
Some standard enthalpies of formation at 298.15 K

FIGURE 7-19
Standard enthalpy of formation of formaldehyde, HCHO(g)

Standard Enthalpies of Reaction
∆Hoverall = –2∆HfºNaHCO3+
∆HfºNa2CO3+
∆HfºCO2 +
∆HfºH2O
FIGURE 7-20
Computing heats of reaction from standard enthalpies of formation

∆Hº = ∑p∆Hfº (products) −∑r∆Hfº (reactants) (7.22)
FIGURE 7-21
Diagramatic representation of equation (7.21)

Reactions Involving Ions in Solution

7-9 Fuels as Sources of Energy
Fossil fuels.
Combustion is exothermic.
Non-renewable resource.
Environmental impact.

FIGURE 7-22
World primary energy consumption by energy source

FIGURE 7-23
The “greenhouse” effect

FIGURE 7-24
Increasing carbon dioxide concentration of the atmosphere

Coal and Other Energy Sources
Gasification of Coal Ethanol
steam and heated coal mostly from ethylene but also by
Liquifaction of Coal fermentation
convert coal gas to long chain Biofuels
hydrocarbons using catalysis biodiesel is composed of methyl
esters of fatty acids
Methanol Hydrogen
prepared from coal or thermal excellent fuel but requires a good
decomposition of various organic production method
materials

7-10 Spontaneous and Nonspontaneous
Processes: An Introduction
spontaneous process
occurs in a system left to itself; once started, no external action is
necessary to make the process continue.
nonspontaneous process
will not occur unless some external action is continuously applied.

spontaneous processes
may be endothermic or exothermic

If a process is spontaneous, the reverse process is nonspontaneous
Both spontaneous and nonspontaneous processes are possible, but

only spontaneous processes will occur without intervention.
Some spontaneous processes occur very slowly, and others

occur rather rapidly.
Some spontaneous processes are exothermic, and others are

endothermic.

End of Chapter

Petrucci 11e PPT Ch07

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GENERAL CHEMISTRY

PRINCIPLES AND MODERN APPLICATIONS

PETRUCCI HERRING MADURA BISSONNETTE

Slide 7 - 1 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 2 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 3 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 4 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 5 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Heat and Work

Slide 7 - 7 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Heat “flows” from hotter to colder.

Slide 7 - 8 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 9 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 10 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Specific heat capacity, cp.

Slide 7 - 11 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

In interactions between a system and its

Slide 7 - 12 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 13 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 15 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 16 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 17 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 18 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

qcal = q bomb + q water + q wires +…

Define the heat capacity of the

Slide 7 - 19 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 20 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Gas formed pushes against the

Slide 7 - 22 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

• Translational kinetic energy.

Slide 7 - 23 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

A system contains only internal energy.

Slide 7 - 24 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

The energy of an isolated system is constant

Slide 7 - 25 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 26 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Water at 293.15 K and 100 kPa is in a specified state.

This density is a unique function of the state.

Slide 7 - 27 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

∆U has a unique value between

Slide 7 - 28 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Consider process in Example 7.5 and Figure 7-8

let us consider a two step process from

Slide 7 - 29 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

= −0.61 L atm – 0.82 L

Compared −1.24×102 J for

Slide 7 - 30 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 31 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 32 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

In a system at constant volume (bomb calorimeter):

But we live in a constant pressure world!

Slide 7 - 33 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

We know that w = –P∆V and ∆U = qv, therefore:

qP = ∆U + P∆V ∆U = ∆H– P∆V

w = P∆V = P(Vf – Vi)

2 CO (g) + O2 (g) 2 CO2 (g) ΔH = –566 kJ mol–1

per mole of reaction

one mole of reaction refers to the situation in

C12H22O11 (g) + 12 O2 (g) 12 CO2 (g) + 11 H2O (g)

Slide 7 - 36 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

No simple physical or molecular interpretation.

Slide 7 - 37 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Molar enthalpy of fusion: