Chem 16 General Chemistry 1

08 Thermochemistry

Dr. Gil C. Claudio

First Semester 2014-2015
Table of Contents

Contents
1 Terminology in Thermochemistry

2 Forms of Energy and their Interconversion

3 Heats of Reaction and Chemical Change

4 First Law of Thermodynamics

5 Heats of Reaction: U and H

6 Stoichiometry of Thermochemical Equations

7 Hesss Law

10

8 Standard Enthalpies of Formation f H

10

9 Bond Energies

11

10 Born-Haber Cycle

12

11 Entropy and Entropy Change

13

12 Evaluating Entropy and Entropy Changes

15

13 Second Law of Thermodynamics

16

14 Standard Gibbs Energy Change

18

15 Gibbs Energy and Temperature

18

References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffy D. Madura, and Carey Bisonnette.
Chemistry: The Central Science, 13th ed., by Theodore L. Brown, H. Eugene
LeMay Jr., Bruce E. Bursten, Catherine J. Murphy, Patrick M. Woodward,
and Matthew W. Stoltzfus.

1 Terminology in Thermochemistry
Thermochemistry
Thermochemistry (orchemical thermodynamics) is the branch of
chemistry concerned with the interrelation of heat and work that accompany
chemical reactions.
It is a subfield of a larger discipline called thermodynamics.
the application of mathematical methods to the study of chemical
questions and the spontaneity of processes.
Internal Energy
Internal energy is the total of all molecular energies, kinetic plus potential,
that are internal to a substance. It includes
Kinetic energy of translation
Kinetic energy of rotation
Kinetic energy of vibration
Potential energy within molecules (bonds)
Potential energy between molecules (IFA)
System, Surrounding, and Boundary
A thermodynamic system (or physical system) is a precisely defined
macroscopic region of the universe that is studied using the principles of
thermodynamics.
SURROUNDINGS

SYSTEM

BOUNDARY

en.wikipedia.org/wiki/File:System boundary.svg

System, surroundings, and boundary

The surroundings (environment, reservoir) represent that portion of the
universe with which a system interacts. All space in the universe outside
the thermodynamic system is the the surroundings.
A system is separated from its surroundings by a boundary (or wall)
which by convention delimits a finite volume. It may be notional or real.
Walls and Constraints
A boundary (or wall) separates the system from the surrounding.
Processes are associated with a redistribution of some quantity within
the system or between the system and surroundings. These quantities
are either matter, work, or heat.
Walls prevent or permit the redistributions of these quantities. Walls are
therefore restrictive or nonrestrictive with respect to these quantities.

Types of Systems
As thermodynamics is fundamentally concerned with the flow and balance
of matter and energy (work and/or heat). Systems are distinguished
depending on the kinds of interaction they undergo and the types of energy
they exchange with the surrounding environment.
System
Isolated
Closed
Open
Partly closed
Adiabatic
Diabatic

Condition
Matter and energy may not cross boundary
Matter may not cross boundary
Heat, work, and matter may cross boundary
Semi-permeable, matter may cross boundary
Heat may not cross boundary
Heat may cross boundary

2 Forms of Energy and their Interconversion

Energy and Work
R
Work is done when a force acts through a distance. W = ~F d~r.
Energy is the capacity to do work.
Kinetic energy is the energy of a moving object. KE = 21 mv2
Potential energy is stored energy, and thus has the potential to do work.
It results from condition, position, and composition.
Energy can change between potential and kinetic.
Mechanical energy is transferred from one object to another through work.
Heat and Temperature
Temperature is a measure of the average translational kinetic energy per
molecule in a substance, measured in degrees Celsius or Fahrenheit or Kelvins.
Heat q is a transfer of thermal energy as a result of a temperature difference.
Energy that passes from a warmer body to a colder body is transferred
as heat, until temperatures become equal. Temperature and phase may
change in the process.
Units of Heat
Calorie is the quantity of heat required to change the temperature of one
gram of water by one degree Celsius.
Joule is the SI unit for heat.

m2
s2
1 cal = 4.184 J
1 J = 1kg

Heat Capacity
The heat capacity C of a system is the quantity of heat required to change
the temperature of a system by one degree.
q = CT
Molar heat capacity - if the system is one mole of a substance.

 Specific heat c (or specific heat capacity) is the heat capacity per gram of
a substance.
q = mcT
The specific heat of water is 4.18 J/(g C)
Law of Conservation of Energy
The law of conservation of energy states that in interactions between a
system and its surroundings, the total energy remains constant.
energy is neither created nor destroyed.
qsystem + qsurroundings = 0
Thus, the heat gained by the system is lost by the surrounding, and vice versa
qsystem = qsurroundings

Calculating the Quantity of Heat

PHMB 10e, Example 7-1, p 245
How much heat is required to raise the temperature of 7.35 g of water
from 21.0 to 98.0 C. Assume that the specific heat of water is 4.18 J/(g- C)
throughout the temperature range.
ANSWER: 2.36 103 J
Determining a Specific Heat from Experimental Data
PHMB 10e, Example 7-2, pp 246-247
A 150.0 g sample of lead is heated to the temperature of boiling water (100
C). A 50.0 g sample of water is added to a thermally insulated beaker, and
its temperature is found to be 22.0 C. The hot lead is dumped into the cold
water, and the temperature of the final lead-water mixture is 22.8 C. Calculate
the specific heat of lead.
ANSWER: 0.13 J/(g C)
Specific Heats of Some Substances
Solids
Pb(s)
Cu(s)
Fe(s)
S8 (s)
P4 (s)
Al(s)
Mg(s)
H2 O(s)

0.130
0.385
0.449
0.708
0.769
0.897
1.023
2.11

Liquids
Hg(l)
Br2 (l)
CCl4 (l)
CH3 COOH(l)
CH3 CH2 OH(l)

0.140
0.474
0.850
2.15
2.44

H2 O(l)

4.18

Gases
CO2 (g)
N2 (g)
C3 H8 (g)
NH3 (g)

0.843
1.040
1.67
2.06

H2 O(g)

2.08

3 Heats of Reaction and Chemical Change

Chemical Energy
Chemical energy is the energy associated with chemical bonds and
intermolecular attractions.
some of this energy appears in the form of heat.
The heat of reaction qrxn is the quantity of heat exchanged between a system
and its surroundings when a chemical reaction occurs within the system, at
constant temperature.
4

 It is the quantity of heat exchanged between the system and its

surroundings as the system is restored to its initial temperature.
Endothermic and Exothermic
An exothermic reaction is one that produces a temperature increase in an
isolated system or, in a nonisolated system, gives off heat to the surroundings.
heat transfers from system to surrounding
qrxn < 0
In an endothermic reaction, the corresponding situation is a temperature
decrease in an isolated system or a gain of heat from the surroundings by an
isolated system.
heat transfers from surrounding to system
qrxn > 0
Bomb Calorimetry
Heats of reaction are experimentally determined in a calorimeter, which is
a device for measuring quantities of heat.
A bomb calorimeter is ideally suited for measuring the heat evolved in
a combustion reaction.
qrxn
qcal

= qcal
= qbomb + qwater + qwires + . . .

The heat capacity of the calorimeter Ccal

qcal = Ccal T
Determining T, we determine qcal , and thus establish qrxn .
Determining the Heat of a Reaction
PHMB 10e, Example 7-3, p 250
The combustion of 1.010 g of sucrose, C12 H22 O11 , in a bomb calorimeter
causes the temperature to rise from 24.92 C to 28.33 C. The heat capacity of
the calorimeter assembly is 4.90 kJ/ C.
1. What is the heat of combustion of sucrose expressed in kJ/mol of
C12 H22 O11 ?
2. Verify the claim of sugar producers that one teaspoon of sugar ( 4.8 g)
contains only 19 Calories
ANSWER:
1. qrxn = 5.65 103 kJ/mol C12 H22 O11
2. Sugar contains -19 kcal/tsp, so the claim is justified.
The Coffee-Cup Calorimeter
We mix the reactants (generally in aqueous solution) in a Styrofoam cup
and measure the temperature change.
Styrofoam is a good heat insulator, so there is very little heat transfer
between the cup and the surrounding air. We treat the cup and its
contents as an isolated system.
qrxn = qcal

Heat of Reaction from Calorimetric Data

PHMB 10e, Example 7-3, p 250
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
H+ (aq) + OH (aq) H2 O(l)
Two solutions, 25.00 mL of 2.50 M HCl(aq) and 2.50 M of NaOH(aq), both
initially at 21 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 H2 O formed Is the reaction endothermic or
exothermic?
ANSWER: qneutr = -56 kJ/mol H2 O
Work
In addition to heat effects chemical reactions may also do work.
Gas formed pushes against the atmosphere. The volume changes.
Pressure-volume work.
Mechanical work
w = F d = M g h
PV-work
w=

Mg
hA = Pext V
A

2 KClO3 (s) 2 KCl(s) + 3 O2 (g)

Calculating Pressure-Volume Work
PHMB 10e, Example 7-5, p 254
Suppose the gas is 0.100 mol He at 298 K, with two external pressures
of 2.40 atm and 1.20 atm. Using w = PV, how much work, in joules, is
associated with the gas expansion at constant temperature?
ANSWER: 1.24 102 J

4 First Law of Thermodynamics

Internal Energy
Internal energy U is the total of all molecular energies, kinetic plus
potential, that are internal to a substance.
KE translation, rotation, vibration
PE within molecules (chemical bonds) between molecules (IFA).
Includes the energy associated with electrons in atoms, and the
interactions of protons and neutrons in atomic nuclei.
The Law of Conservation of Energy
The law of conservation of energy states that energy can neither be created
nor destroyed in ordinary processes.
only changes form, like between q and w.
The energy of an isolated system is constant, Uisolated system = 0

Conventions
endothermic, heat is absorbed by the system, q > 0
exothermic, heat released by the system, q < 0
work done on the system, w > 0
work done by the system, w < 0
If energy enters the system, U > 0.
If energy leaves the system, U < 0.
Uisolated system = 0 Usystem = Usurroundings
Relating U, q, and w
PHMB 10e, Example 7-6, p 256
A gas, while expanding, absorbs 25 J of heat and does 243 J of work. What
is U for the gas?
ANSWER: -218 J
Functions of State
To describe a system completely, we must indicate its temperature T,
pressure P, volume V, and the kinds and amounts of the substances present
ni . These variables are called state variables.
Any property that has a unique value for a specified state of a system is
said to be a state function.
Independent on how that state was established. Path independent.
Other names: state functions, function of state, state quantity, or
thermodynamics coordinates.
e.g., internal energy, enthalpy, and entropy.
U as a Function of State
The internal energy of a system U is a function of state, although there
is no simple measurement or calculation that we can use to establish this value.
The difference in internal energy U = U2 U1 has a unique value
between two states and is something we can measure precisely.
Equation of State
An equation of state is a thermodynamic equation describing the state of
matter under a given set of physical conditions.
It is a mathematical relationship between two or more state functions.
e.g., PV = nRT.
Path-Dependent Functions
Unlike internal energy and changes in internal energy, heat q and work w
are not functions of state.
These are process quantities (path dependent).
Reversible and Irreversible Processes
A reversible process is one that can be made to reverse direction by just an
infinitesimal change in a system property.
An irreversible process takes place in one or several finite steps such
that the system is not in equilibrium with its surroundings.
7

5 Heats of Reaction: U and H

Internal Energy of Reaction
Given the internal energies in a reaction
reactants products
Ui

Uf

U = U f Ui
Relating to the first law
U = qrxn + w

Constant Volume and Constant Pressure Processes

Bomb calorimeter
constant V V = 0
w = PV = 0
UV = qV
Constant pressure
UP = q P + w
Path independent, thus
UV = UP

Enthalpy
Since UV = UP , then for processes at constant P
qV = q P + w

U = q P PV

q P = U + PV

Since U, P, and V are state functions, then U + PV is also a state function

called enthalpy H. The change in enthalpy is
H

= U + ( PV )
= U + PV = q P

at constant P

At constant P,
H = U + PV = q P

and

U = H PV

U and H in CO2
Given the reaction
2 CO2 (g) + O2 (g) 2 CO2 (g)
The heat of the reaction at constant pressure at 298 K is H = 566.0 kJ.
Using the ideal gas law, PV = 2.5 kJ, and thus U = 566.0 kJ + 2.5 kJ =
563.5 kJ.

U and H in Sucrose
The molar enthalpy change in the combustion of sucrose is H = 5.65
103 kJ.
C12 H22 O11 (s) + 12 O2 (g) 12 CO2 (g) + 11 H2 O(l)
Here, qV = q P since there is no change in volume.
From Example 7-7 (p 263), the complete combustion of 1 kg of sucrose
involves 1.65 104 kJ.
H and Changes in State
Molar enthalpy of vaporization
H = 44.0 kJ at 298 K

H2 O(l) H2 O(g)
Molar enthalpy of fusion
H2 O(s) H2 O(l)

H = 6.01 kJ at 273.15 K

Standard States and Standard H

Define a particular state as a standard state.
The standard state of a substance refers to that substance when it is
maintained at 1 bar (105 Pa) pressure and at the temperature of interest.
The standard enthalpy of reaction H is the enthalpy change of a reaction in
which all reactants and products are in their standard states.
Enthalpy Changes in Changes in States
PHMB 10e, Example 7-8, p 264
Calculate H for the process in which 50.0 g of water is converted
from liquid at 10.0 C to vapor at 25.0 C. Note that the molar enthalpy of
vaporization at 25.0 C is 44.0 kJ/mol.
ANSWER: 125 kJ
Enthalpy Diagram
An enthalpy diagram is a diagrammatic representation of enthalpy
changes in a process

6 Stoichiometry of Thermochemical Equations

PLEASE RESEARCH
Thermochemical Equations
The enthalpy change that accompanies a reaction is called the enthalpy of
reaction (or the heat of reaction) r H.
Balanced chemical equations that show the associated enthalpy change
in this way are called thermochemical equations.

Rules in Thermochemical Equations

1. H is an extensive property.
N2 (g) + O2 (g) 2 NO(g)
N2 (g) + 21 O2 (g) NO(g)

1
2

H = 180.50 kJ
H = 90.25 kJ

2. H change sign when a process is reversed

NO(g)

1
2

N2 (g) +

1
2

O2 (g)

H = -90.25 kJ

3. The enthalpy change for a reaction depends on the states of the reactants
and products.
2 H2 O(l) 2 H2 O(g)

H = +88 kJ

7 Hesss Law
Hesss Law
Hesss Law states that the enthalpy change for an overall or net process is
the sum of enthalpy changes for individual steps in the process.
Hesss Law of Constant Heat Summation
N2 (g) + 12 O2 (g) NO(g)
NO(g) + 21 O2 (g) NO2 (g)
1
2 N2 (g) + O2 (g) NO2 (g)
1
2

H = 90.25 kJ
H = -57.07 kJ
H = 33.18 kJ

Applying Hesss Law

PHMB 10e, Example 7-9, p 256
Determine the H for the reaction
3 C (graphite) + 4 H2 (g) C3 H8 (g)

H = ?

using the following data

C3 H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2 O(l)
C(graphite) + O2 (g) CO2 (g)
H2 (g) + 12 O2 (g) H2 O(l)

H = -2219.9 kJ
H = -393.5 kJ
H = -285.8 kJ

ANSWER: H = -104 kJ

8 Standard Enthalpies of Formation f H

Standard Enthalpies of Formation
The standard enthalpy of formation f H f of a substance is the enthalpy
change that occurs in the formation of one mole of the substance in the
standard state from the reference forms of the elements in their standard states.
The reference forms of the elements in all but a few cases are the most
stable forms of the elements at one bar and the given temperature.
The standard enthalpy of formation of a pure element in its reference state is 0.
The most stable forms of the following elements at 298.15 K: Na(s), H2 (g),
N2 (g), O2 (g), C (graphite), Br2 (l)

10

Standard Enthalpies of Reaction

One of the primary uses of standard enthalpies of formation is in
calculating standard enthalpies of reaction.
The standard enthalpy of reaction r H is the enthalpy change of a
reaction in which all reactants and products are in their standard states.
r aH =

vP f H (products) vR f H (reactants)

f H : An Example
Decomposition of sodium bicarbonate, a minor reaction that occurs when
baking soda is used in baking.

reaction
2 NaHCO3 (s) 2 Na(s) + H2 (g)
+ 2 C(graphite) + 3 O2 (g)
2 Na(s) + C(graphite) + 32 O2 (g)
Na2 CO3 (s)
H2 + 21 O2 (g) H2 O(l)
C(graphite) + O2 (g) CO2 (g)
2 NaHCO3 (s) Na2 CO3 (s)
+ H2 O(l) + CO2 (g)

H
-2 H f [NaHCO3 (s)]
H f [Na2 CO3 (s)]
H f [H2 O(l)]
H f [CO2 (g)]
H = ?

Ionic Reactions in Solution

In order to have a table of H f for ions, we must choose a particular ion
to which we assign an enthalpy of formation of zero in its aqueous solutions.
The ion we arbitrarily choose for our zero is H+ (aq).
From experiment
H+ (aq) + OH (aq) H2 O(l)

H = -55.8 kJ/mol

Since H f [H2 O(l)] = -285.8 kJ/mol and H f [H+ (aq)] = 0 kJ/mol, then
H f [OH (aq)] = -230.0 kJ/mol
H in an Ionic Reaction
PHMB 10e, Example 7-13, p 274
Given that H f [BaSO4 (s)] = -1473 kJ/mol, what s the standard enthalpy
change for the precipitation of barium sulfate? From the table, H f [Ba2+ (aq)]
= -537.6 kJ/mol and H f [SO42 (aq)] = -909.3 kJ/mol.
ANSWER: -26 kJ/mol

9 Bond Energies
Bond-Dissociation Energy
Bond-dissociation energy, D, is the quantity of energy required to break
one mole of covalent bonds in a gaseous species, usually expressed in kJ/mol.

11

Some Average Bond Energies

bond
HH
HC
HN
HO
HS
HF
HCl
HBr
HI

bond energy
kJ/mol
436
414
389
464
368
565
431
364
297

bond
CC
CC
C
C
CN
CN
C
N
CO
CO
CCl

BDE for Diatomic Molecules

bond breakage
H2 (g)
bond formation

2 H(g)

bond energy
kJ/mol
347
611
837
305
615
891
360
736
339

bond
NN
NN
N
N
NO
NO
OO
OO
FF
ClCl
BrBr
II

bond energy
kJ/mol
163
418
946
222
590
142
498
159
243
193
151

2 H(g)
H = D(HH) = +435.93 kJ/mol
H2 (g)
H = D(HH) = -435.93 kJ/mol

BDE for Polyatomic Molecules

An average bond energy is the average of bond-dissociation energies for a
number of different species containing a particular covalent bond.
HOH(g)
OH(g)

H(g) + OH(g)
H(g) + O(g)

H = D(HOH) = +498.8 kJ/mol

H = D(OH) = +428.0 kJ/mol

The average bond energy for OH is 464 kJ/mol.

For methanol CH3 OH, D(HOCH3 ) = 436.8 kJ/mol.
Higher Bond Order Bond Energies
Bond energies of higher order bonds are greater than those of lower bond
orders.
Double bonds have higher bond energies than do single bonds between
the same atoms, but they are not twice as large.
Triple bonds are stronger still, but their bond energies are not three times
as large as single bonds between the same atoms.
from Bond Energies
Calculating Hrxn
PHMB 10e, Example 10-15, p 436
The reaction of methane CH4 and chlorine produces a mixture of products
called chloromethanes. One of these is monochloromethane CH3 Cl used in the
reaction
preparation of silicones. Calculate for the Hrxn

CH4 (g) + Cl2 (g) CH3 Cl(g) + HCl(g)

ANSWER: -113 kJ
Endothermic/Exothermic from BDE
Another way to use bond energies is in predicting whether a reaction will
be endothermic or exothermic. In general,
weak bonds
(reactants)

strong bonds
(products)

H < 0 exothermic

strong bonds
(reactants)

weak bonds
(products)

H > 0 endothermic

and

12

10

Born-Haber Cycle

Lattice Energy
Lattice energy is the quantity of energy released in the formation of one
mole of a crystalline ionic solid from its separated gaseous ions.
Li+ (g) + F (g) LiF(s)

0 = lattice energy = -1050 kJ

HLiF

The lattice energy is an important indication of the strength of ionic

interactions and is a major factor in influencing melting points, hardness,
and solubilities of ionic compounds.
Lattice energies can be calculated through a Born-Haber cycle, which
is a series of steps from elements to ionic compounds for which all the
enthalpies are known except the lattice energy.
Born-Haber Cycle for LiF
Given that all the other energies are experimentally available
Li(s)
F2 (g)
Li(g)
F(g)
+
Li (g) + F (g)
Li(s) + 12 F2 (g)
1
2

Li(g)
F(g)
Li+ (g)
F (g)
LiF(s)
LiF(s)

H 0 = atomization = 161 kJ
H 0 = 21 bond energy = 79.5 kJ
H 0 = IE1 = 520 kJ
H 0 = EA = -328 kJ
0 = lattice energy = ?
HLiF
0 = formation = -617 kJ
HLiF

0 = -1050 kJ/mol.
The lattice energy is computed as HLiF

11

Entropy and Entropy Change

Spontaneity
A spontaneous process is a process that is able to take place in a system left
to itself.
No external action is required to make the process go.
In some cases the process may take a very long time. E.g., rusting of iron.
A nonspontaneous process is one that will not occur naturally.
A nonspontaneous process can be brought about only by intervention
from outside the system, as in the use of electricity to decompose a
chemical compound (electrolysis).
Spontaneity: Some Conclusions
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. E.g., the melting of ice at 1 C and at 99 C. E.g., rusting of iron.
H is not the criteria of spontaneity. Some spontaneous endothermic
processes are the melting of ice at room temp, and the dissolving of
ammonium nitrate in water.

13

Free Expansion of a Gas

Consider the free expansion of an ideal gas at constant T
U does not depend on P, thus U = 0
PV = constant, thus H = 0
The same is true for the mixing of an ideal gas.

Entropy
Entropy S is a thermodynamic property related to the number of energy
levels among which the energy of the system is spread.
The greater the number of energy levels for a given total energy, the
greater the entropy.
The greater the number of arrangements (or microstates) of the
microscopic particles (atoms, ions, molecules) among the energy levels
in a particular state of a system, the greater the entropy of a system.
There is a unique value of S for a system whose T, P, and ni are specified.
Entropy change S is the difference in entropy between two states of a system.
The S between two states also has a unique value.
Increases in entropy underlie spontaneous processes.
The Boltzmann Equation for Entropy
Ludwig Boltzmann associated the number of energy levels in a system with
the number of ways of arranging the particles in these energy levels.
The microscopic energy levels are called states and the particular way
a number of particles is distributed among these states is called a
microstate.
The Boltzmann equation
S = k ln W
where S is entropy, k is the Boltzmann constant and W is the number of
microstates.
The Microscopic and Macroscopic Pictures
The state of a thermodynamic system can be described in two ways:
1. the macroscopic description, in terms of state functions P, V, and T
2. the microscopic description, requiring the knowledge of position and
velocity of every particle in the system.
Boltzmanns equation provides the connection between the two.
Entropy Change
Entropy change is based on two measurable quantities: heat (q) and
temperature (T, in K), and are related via
S =

qrev
T

This equation holds only if the path from initial to final states is reversible.

14

Qualitative Predictions on S (1)

An increase (or decrease) in the accessibility of energy levels depends on
the number of microscopic particles and the space available to them.

Qualitative Predictions on S (2)

Four situations generally produce an increase in entropy
Pure liquids or liquid solutions are formed from solids.
Gases are formed from either solids or liquids.
The number of molecules of gas increases as a result of a chemical
reaction.
The temperature of the substance increases.
Entropy Change is Processes
PHMB 10e, Example 19-1, p 826
Predict whether each of the following processes involves an increase or a
decrease in entropy or whether the outcome is uncertain.
1. The decomposition of ammonium nitrate (a fertilizer and a highly
explosive compound): 2 NH2 NO3 (s) 2 N2 (g) + 4 H2 O(g) + O2 (g)
2. The conversion of SO2 to SO3 (a key step in the manufacture of sulfuric
acid): 2 SO2 (g) + O2 (g) 2 SO3 (g)
3. The extraction of sucrose from cane sugar juice: C12 H22 O11 (aq)
C12 H22 O11 (s)
4. The water gas shift reaction (involved in the gasification of coal): CO(g)
+ H2 O(g) CO2 (g) + H2 (g)
ANSWERS: increase, decrease, decrease, cannot determine

12

Evaluating Entropy and Entropy Changes

Phase Transitions
In the equilibrium between two phases, the exchange of heat can be carried
out reversibly, and the quantity of heat is equal to the enthalpy of change for
the transition.
Htr
Str =
Ttr
tr can be either fus or vap
For example, the melting (fusion) of ice at its normal melting point
H2 O(s, 1 atm) H2 O(l, 1 atm)

Sfus
=

= 6.02 kJ/mol at 273.15 K

Hfus

Hfus
6.02 kJ/mol
=
= 22.0 J/(mol-K)
Tmp
273.14 K

Troutons Rule
Troutons Rule states that for many liquids at their normal boiling points,
the standard molar entropy of vaporization has the value of about 87
J/(mol-K).

Hvap

87 J/(mol-K)
Svap
=
Tbp
of benzene is 87.1 J/mol-K, and the of S of octane
For example, the Svap
vap
is 86.2 J/mol-K.

15

Determining S for a Phase Transition

PHMB 10e, Example 19-2, p 829
What is the standard molar entropy for the vaporization of water at 373 K
given that the standard molar enthalpy of vaporization is 40.7 kJ/mol.
ANSWER: 109 J/mol-K
Absolute Entropies
To establish an absolute value of the entropy of a substance, we look for its
zero point energy (or lowest possible energy state) where its entropy is taken
to be zero.
The Third Law of Thermodynamics can be stated as: the entropy of a
pure perfect crystal at 0 K is zero.
The standard molar entropy S is the absolute entropy of one mole of
substance in its standard state.
S =

vP S (products) vR S (reactants)

Standard Molar Entropies

PHMB 10e, Example 19-3, p 831
Using data from tables, calculate the standard molar entropy change
for the conversion of nitrogen monoxide to nitrogen dioxide (a step in the
manufacture of nitric acid).

S298
K =?

2 NO(g) + O2 (g) 2 NO2 (g)

SNO

2 (g)

= 240.1 J/K, SNO

(g) = 210.8 J/K, and SO

2 (g)

= 205.1 J/K.

ANSWER: -146.5 J/K

13

Second Law of Thermodynamics

Total Entropy
The criteria for spontaneous change must be based not only on the entropy
of the system, but on the sum of the system and surrounding
Stotal = Suniverse = Ssystem + Ssurroundings
In a spontaneous (irreversible) change
Suniv = Ssys + Ssurr > 0
In a reversible reaction
Suniv = Ssys + Ssurr = 0

Melting of Ice
The entropy change in the irreversible melting of 1 mol of ice
Ssys =

qrev
(1 mol)(6.01 103 J/mol)
=
= 22.0 J/K
T
273 K

16

The surroundings immediately in contact with the ice are your hand (T =
37 C), which therefore loses 6.01 103 J/mol. Thus the entropy change of
the surrounding is
qrev
(1 mol)(6.01 103 J/mol)
=
= 19.4 J/K
T
310 K
Therefore the overall entropy change of the universe is
Ssurr =

Suniv = Ssys + Ssurr = 2.6 J/K

Suniv 0 only if T1 T2 , which is the condition for reversibility.
Second Law of Thermodynamics
The second law of thermodynamics states that in a spontaneous change,
Suniv = Ssys + Ssurr > 0
Another statement of the second law is: all spontaneous processes produce an
increase in the entropy of the universe.
Spontaneity Using System Variables
Given a process conducted at constant T and P and with work limited to
PV work. Assuming also that the path by which heat enters or leaves the
surroundings is reversible.
qsurr = q P = Hsys

Ssurr =

Hsys
T

We get an equation involving only the system

TSuniv = TSsys Hsys = (Hsys TSsys )
Thus for spontaneity
Suniv > 0

Hsys TSsys < 0

Gibbs Energy and Spontaneity

The previous equation leads us to a new thermodynamic function, called
the Gibbs Energy G
G = H TS
The Gibbs energy change G, for a process at constant T and P is
G = H TS
where all terms apply to the system.
For a process occurring at constant T and P
If G < 0, the process is spontaneous
If G > 0, the process is nonspontaneous
If G = 0, the process is at equilibrium
The Gibbs Energy Criteria
H
+
+
+

S
+
+
+
-

G
+
+
+

result
spont at all T
spont at low T
nonspont at high T
nonspont at low T
spont at high T
nonspont at all T
17

example
2 NO2 (g) 2 N2 (g) + O2 (g)
H2 O(l) H2 O(s)
same
2 NH3 (g) N2 (g) + 3 H2 (g)
same
3 O2 (g) 2 O3 (g)

The Gibbs Energy Change and Work

The criteria for spontaneity is G and not H.
In a process, the quantity of heat H must be adjusted for the heat
requirement in producing entropy change in the system.
The amount of work that can be extracted from a chemical process is G.
Since G represents the energy freely available for doing work, G was
once called Gibbs free energy or simply free energy by most chemists.

14

Standard Gibbs Energy Change

Standard Gibbs Energy Change

Since G is related to H (G = H TS), we cannot establish absolute values
of G. We must work with Gibbs energy changes G.
The standard Gibbs energy of formation G f is the Gibbs energy change
for a reaction in which a substance in its standard state is formed from its
elements in their reference forms in their standard states.
The value of zero is assigned to Gibbs energies of formation of the
elements in their reference forms at a pressure of 1 bar.
Tabulated per mole
Two expressions can be used
G = H TS
G =

or

vP Gf (products) vR Gf (reactants)

Calculating G for a Reaction

PHMB 10e, Example 19-5, p 837
Determine G at 298.15 K for the reaction
2 NO(g) + O2 (g) 2 NO2 (g)
given that H = -114.1 kJ and S = -146.5 J/K at 298.15 K.
ANSWER: -70.4 kJ

15

Gibbs Energy and Temperature

Temperature Dependence of G
Tabulations of G f make it possible to calculate the Gibbs energy for
reactions at the standard temperature of 25 C. The temperature dependence
of G is given by
G = H TS

18

Temperature Dependence of G
H
-

S
+

G
-

spontaneity
spont all T

example
2 O3 (g) 3 O2 (g)

nonspont all T

3 O2 (g) 2 O3 (g)

+ or -

H2 O(l) H2 O(s)

+ or -

spont low T
nonspont high T
spont high T
nonspont low T

H2 O(s) H2 O(l)

Determining the Effect of T on Spontaneity

BLBMWS 13e, Exercise 19.9, pp 837-838
The Haber process for the production of ammonia involves the equilibrium
N2 (g) + 3H2 (g) 2 NH3 (g)
Assume that H and S for this reaction do not change with temperature.
Note that H 92.38 kJ and S = 198.3 J/K.
1. Predict the direction in which G for the reaction changes with
increasing temperature.
2. Calculate G at 25 C and at 500 C.
ANSWERS
1. G becomes less negative at higher T
2. -33 kJ and 61 kJ

19