General Chemistry: Thermochemistry

GENERAL CHEMISTRY
Principles and Modern Applications TENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Thermochemistry 7
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND
BIOCHEMISTRY
Slide 1 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Thermochemistry

6-1 Getting Started: Some Terminology
FIGURE 7-1
Systems and their surroundings
Energy, U
The capacity to do work.
Work, w
Force acting through a distance.
Kinetic Energy, eK
The energy of motion.
Potential Energy, V
The stored energy has potential to do work.

Kinetic Energy
2
1 m
ek = mv 2
[ek ] = kg = J
2 s
Work
w=Fxd
m m
= mxaxd [w ] = kg 2 = J
s

Potential Energy
Energy due to condition, position, or
composition.
Associated with forces of attraction or repulsion
between objects.
Energy can change from potential to kinetic.

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

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

EXAMPLE 7-1
How much heat is required to raise the temperature of 7.35 g of water
from 21.0 to 98.0 ºC (Assume the specific heat of water is
4.18 J g-1 ºC-1 throughout this temperature range.)?
HW: 7-A, 7-B
FIGURE 7-3
Determining the specific heat of lead – Example 7-2 illustrated

Heat Capacity
The quantity of heat required to change the

temperature of a system by one degree.
Molar heat capacity.

System is one mole of substance.
Specific heat capacity, c. q = mcT
System is one gram of substance
Heat capacity
q = CT
(Mass of system) x specific heat.

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

TABLE 7.1 Some Specific Heat Values, J g-1 °C-1

7-3 Heats of Reaction and Calorimetry
Chemical energy.
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.

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.

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

Bomb Calorimetry
qrxn = -qcal
qcal = q bomb + q water + q wires +…
heat Define the heat capacity of the

calorimeter:
qcal = m
all i iciT = CcalT
FIGURE 7-5
A bomb calorimeter assembly
EXAMPLE 7-3
The combustion of 1.010 g sucrose, C12H22O11 , in a bomb calorimeter

causes the temperature to rise from 24.92 to 28.33 °C. The heat capacity
of the calorimeter assembly is 4.90 kJ/°C. (a) What is the heat of
combustion of sucrose expressed in kilojoules per mole of C12H22O11?
(b) Verify the claim of sugar producers that one teaspoon
of sugar (about 4.8 g) contains only 19 Calories.
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
EXAMPLE 7-4
In the neutralization of a strong acid with a strong base, the
essential reaction is the combination of H+(aq) and OH-(aq) to form
water
Two solutions, 25.00 mL of 2.50 M HCl(aq) and 25.00 mL of 2.50

M NaOH(aq), both initially at 21.1 °C, are added to a Styrofoam-
cup calorimeter and allowed to react. The temperature rises to
37.8 °C. Determine the heat of the neutralization reaction,
expressed per mole of H2O formed. Is the reaction endothermic or
exothermic?
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 O 2(g)

w=Fxd
= (m x g) x h
(m x g)
=  h x 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
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
Law of Conservation of Energy

The energy of an isolated system is constant

The First Law of Thermodynamics
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 1.00 atm 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.

Functions of State
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.
Remember example 7-5,
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.

Path Dependent Functions
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
7-6 Heats of Reaction: U and H
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?
FIGURE 7-13
Two different paths leading to the same internal energy change in a system

Heats of Reaction
qV = qP + w
We know that w = - PV and U = qv, therefore:
U = qP - PV
qP = U + PV
These are all state functions, so define a new function.
Let enthalpy be H = U + PV
Then H = Hf – Hi = U + PV
If we work at constant pressure and temperature:
H = U + PV = qP

Comparing Heats of Reaction
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
FIGURE 7-14
Comparing heats of reaction at constant volume and constant pressure for
the reaction 2 CO(g) + 2 O2(g) 2 CO2(g)
Slide 37 of 57
General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.
Enthalpy Change () Accompanying a
Change in State of Matter
Molar enthalpy of vaporization:
H2O (l) → H2O(g) H = 44.0 kJ at 298 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, H°
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.

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
½N2(g) + ½O2(g) → NO(g) H° = +90.25 kJ
• H changes sign when a process is reversed

NO(g) → ½N2(g) + ½O2(g) H° = -90.25 kJ

Hess’s Law Schematically

• Hess’s law of constant heat summation
½N2(g) + O2(g) → NO(g) + ½ O2 (g) H° = +90.25 kJ

NO(g) + ½O2(g) → NO2(g) H° = -57.07 kJ
½N2(g) + O2(g) → NO2(g) H° = +33.18 kJ
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 Hf°
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 of a pure

element in its reference state is 0.

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

Diamond and graphite

Standard Enthalpy of Formation

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

Standard Enthalpies of Reaction
Hoverall = -2Hf°NaHCO3+ Hf°Na2CO3

+ Hf°CO2 + Hf°H2O
FIGURE 7-20
Computing heats of reaction from standard enthalpies of formation
∆H° = ∑p∆Hf°(products) - ∑r∆Hf°(reactants) (7.21)
FIGURE 7-21
Diagramatic representation of equation (7.21)

Ionic Reactions in Solutions

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

Global Warming – An Environmental Issue Involving Carbon Dioxide
eu m
t r ol
pe
coal a s
ra l g
natu wind
nuclear
FIGURE 7-22
World primary energy consumption by energy source
FIGURE 7-23
The “greenhouse” effect

Global average atmospheric Actual and predicted CO2
carbon dioxide level emissions
a g e
ver
al A
l ob
G

Coal and Other Energy Sources
Gasification of Coal Ethanol

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

End of Chapter Questions
Seek help with problems

But only after struggling with them.
The initial effort pays off
Understanding occurs when solutions are
explained by peers, tutors or professors.
Do not go straight to the solution manual
You only think that you understand the solution if
you have not worked hard on it first. The
struggle to solve the problem is a key part of
the memory and understanding process.

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GENERAL CHEMISTRY

Principles and Modern Applications TENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Slide 1 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 2 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 4 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 5 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Energy can change from potential to kinetic.

Slide 6 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 7 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 8 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Heat “flows” from hotter to colder.

Slide 9 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 10 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 12 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

The quantity of heat required to change the

Molar heat capacity.

Slide 13 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

In interactions between a system and its

Slide 14 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 15 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 16 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 17 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 18 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 19 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

qcal = q bomb + q water + q wires +…

heat Define the heat capacity of the

The combustion of 1.010 g sucrose, C12H22O11 , in a bomb calorimeter

Two solutions, 25.00 mL of 2.50 M HCl(aq) and 25.00 mL of 2.50

Gas formed pushes

FIGURE 7-7 Illustrating work (expansion) during the chemical reaction

Slide 24 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 25 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

•Translational kinetic energy.

A system contains only internal energy.

Law of Conservation of Energy

Slide 27 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

An isolated system is unable to exchange either

The energy of an isolated system is constant.

Slide 28 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 29 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Any property that has a unique value for a

Water at 293.15 K and 1.00 atm is in a specified

Slide 30 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

U has a unique value

Slide 31 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Changes in heat and work are not functions

let us consider a two step process from

Slide 32 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

= -0.61 L atm – 0.82 L atm

Compared -1.24  102 J

In a system at constant volume (bomb calorimeter):

But we live in a constant pressure world!

Slide 35 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 36 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

w = PV = P(Vf – Vi)

H2O (l) → H2O(g) H = 44.0 kJ at 298 K

Molar enthalpy of fusion: