Thermodynamics and Equilibrium: Adapted by B Kuswandi From The Internet Open Sources

Thermodynamics
and Equilibrium
Adapted by B Kuswandi from the

internet open sources
Thermodynamics
Thermodynamics is the study of the

relationship between heat and other forms of
energy in a chemical or physical process.
We introduced the thermodynamic property of
enthalpy, H.
We noted that the change in enthalpy equals
the heat of reaction at constant pressure.
In this lecture we will define enthalpy more
precisely, in terms of the energy of the system.
Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 2

First Law of Thermodynamics
To state the laws of thermodynamics, we

must first understand the internal energy of
a system and how you can change it.
The internal energy, U, is the sum of the
kinetic and potential energies of the particles
making up the system.
Internal energy is a state function. That is, a
property of a system that depends only on its
present state.


Thus, 1 mol of water at 0 oC and 1 atm pressure
has a definite quantity of energy.
When a system changes from one state to
another, its internal energy changes.
U  U final  U initial

Changes in U manifest themselves as
exchanges of energy between the system and
surroundings.
These exchanges of energy are of two kinds;
heat and work.


Heat is energy that moves into or out of a
system because of a temperature difference
between system and surroundings.
Work, on the other hand, is the energy
exchange that results when a force F moves an
object through a distance d; work (w) = Fd

Remembering our sign convention.
Work done by the system is negative.
Work done on the system is positive.
Heat evolved by the system is negative.
Heat absorbed by the system is positive.


The distinction between heat and work.
The system gains internal energy from the heat

absorbed and loses internal energy via the work
done.


In general, the first law of thermodynamics
states that the change in internal energy, U ,
equals heat plus work.
U  q  w

Heat of Reaction and Internal
Energy
When a reaction is run in an open vessel
(at constant P), any gases produced repr
esent a potential source of
“expansion” work.
When gases are produced, they exert force on
the surroundings as pressure.
If the reaction is run at constant pressure, then
the gases produced represent a change in
volume analogous to a distance over which a
force is exerted.
Energy
When a reaction is run in an open vessel (at
constant P), any gases produced represent a
potential source of “expansion” work.
It follows therefore, that
w   PV
You can calculate the work done by a chemical
reaction simply by multiplying the atmospheric
pressure by the change in volume, V.

Energy
For example, when 1.00 mol Zn reacts with excess
HCl, 1.00 mol H2 is produced.
Zn(s )  2H 3O  (aq)  Zn 2 (aq )  H 2 (g ) qp = -152.4 kJ

Energy
At 25 oC and 1.00 atm (1.01 x 105 Pa), this
amount of H2 occupies 24.5 L (24.5 x 10-3m3).
Zn(s )  2H 3O  (aq)  Zn 2 (aq )  H 2 (g ) qp = -152.4 kJ

Energy
The work done by the chemical system in
pushing back the atmosphere is
5 3 3
w   PV  (1.01  10 Pa )  ( 24.5  10 m )
3
 2.47  10 J or - 2.47 kJ

Energy
Relating the change in internal energy to the
heat of reaction, you have
U  q p  w
U  ( 152.4 kJ )  ( 2.47 kJ )
U  154.9 kJ
Energy
When the reaction occurs, the internal energy
changes as the kinetic and potential energies
change in going from reactants to products.
Energy leaves the system mostly as heat
(qp = -152.4 kJ) but partly as expansion
work (-2.47 kJ).
Enthalpy and Enthalpy Change
In this lecture, we tentatively defined

enthalpy in terms of the relationship of H
to the heat at constant pressure.
We now define enthalpy, H , precisely as the
quantity U + PV.
Because U, P, and V are state functions, H is
also a state function.


This means that at a given temperature and
pressure, a given amount of a substance has a
definite enthalpy.
Therefore, if you know the enthalpies of
substances, you can calculate the change in
enthalpy, H , for a reaction.


In practice, we measure certain heats of
reactions and use them to tabulate enthalpies of
formation, Hof.
Standard enthalpies of formation for selected
compounds are listed in Table listed in the
Handbook (PW Atkin) and in the Appendix.


The standard enthalpy change for a reaction is
H o   nH of (products)   mH of (reactants)

Spontaneous Processes and
Entropy
A spontaneous process is a physical or
chemical change that occurs by itself.
Examples include:
A rock at the top of a hill rolls down.
Heat flows from a hot object to a cold one.
An iron object rusts in moist air.
These processes occur without requiring an
outside force and continue until equilibrium
is reached.
Entropy and the Second Law of
Thermodynamics
The second law of thermodynamics
addresses questions about spontaneity in
terms of a quantity called entropy.
Entropy, S , is a thermodynamic quantity that
is a measure of the randomness or disorder of a
system.
The SI unit of entropy is joules per Kelvin
(J/K) and, like enthalpy, is a state function.

Thermodynamics
The second law of thermodynamics states
that the total entropy of a system and its
surroundings always increases for a
spontaneous process.
The net change in entropy of the system, S ,
equals the sum of the entropy created during
the spontaneous process and the change in
energy associated with the heat flow.

Thermodynamics
In other words,
q
S  entropy created 
T
(For a spontaneous process)

Thermodynamics
Normally, the quantity of entropy created
during a spontaneous process cannot be directly
measured.

Thermodynamics
If we delete it from our equation, we can
conclude
q
S 
T
(For a spontaneous process)

Thermodynamics
The restatement of the second law is as follows:
for a spontaneous process, the change in
entropy of the system is greater than the
heat divided by the absolute temperature.

Entropy Change for a Phase
Transition
If during a phase transition, such as ice
melting, heat is slowly absorbed by the
system, it remains near equilibrium as the ice
melts.
Under these conditions, no significant amount
of entropy is created.
The entropy results entirely from the absorption
of heat. Therefore,
q
S  (For an equilibrium process)
T
Entropy Change for a Phase
Transition
If during a phase transition, such as ice
melting, heat is slowly absorbed by the
system, it remains near equilibrium as the ice
melts.
Other phase changes, such as vaporization of a
liquid, also occur under equilibrium conditions.
Therefore, you can use the previous equation to
obtain the entropy change for a phase change.

A Problem To Consider
The heat of vaporization, Hvap of carbon

tetrachloride, CCl4, at 25 oC is 43.0 kJ/mol. If 1 mol
of liquid CCl4 has an entropy of 214 J/K, what is the
entropy of 1 mol of the vapor at this temperature?
When liquid CCl4 evaporates, it absorbs heat:
Hvap = 43.0 kJ/mol (43.0 x 103 J/mol) at 25 oC,
or 298 K. The entropy change, S, is
H vap 43.0  103 J / mol
S    144 J/(mol  K )
T 298 K
The heat of vaporization, Hvap of carbon

tetrachloride, CCl4, at 25 oC is 43.0 kJ/mol. If 1 mol
of liquid CCl4 has an entropy of 214 J/K, what is the
entropy of 1 mol of the vapor at this temperature?
In other words, 1 mol of CCl4 increases in entropy
by 144 J/K when it vaporizes.
The entropy of 1 mol of vapor equals the entropy
of 1 mol of liquid (214 J/K) plus 144 J/K.
Entropy of vapor  (214  144)J/K  358 J/(mol  K)

Entropy, Enthalpy, and
Spontaneity
Now you can see how thermodynamics is
applied to the question of reaction spontaneity.
Recall that the heat at constant pressure, qp ,
equals the enthalpy change, H.
The second law for a spontaneous reaction at
constant temperature and pressure becomes
q p H
S   (Spontaneous reaction, constant T and P)
T T
Entropy, Enthalpy, and
Spontaneity
Now you can see how thermodynamics is
applied to the question of reaction spontaneity.
Rearranging this equation, we find
 H  T S  0 (Spontaneous reaction, constant T and P)
This inequality implies that for a reaction to be

spontaneous, H-TS must be negative.
If H-TS is positive, the reverse reaction is
spontaneous. If H-TS=0, the reaction is at
equilibrium
Standard Entropies and the Third
Law of Thermodynamics
The third law of thermodynamics states
that a substance that is perfectly crystalline
at 0 K has an entropy of zero.
When temperature is raised, however, the
substance becomes more disordered as it
absorbs heat.
The entropy of a substance is determined by
measuring how much heat is required to change
its temperature per Kelvin degree.

The standard entropy of a substance or ion
(Please see Handbook), also called its
absolute entropy, So, is the entropy value
for the standard state of the species.
Standard state implies 25 oC, 1 atm pressure,
and 1 M for dissolved substances.

The standard entroy of a substance or ion
Note that the elements have nonzero values,
unlike standard enthalpies of formation, Hfo ,
which by convention, are zero.

The standard entropy of a substance or ion
The symbol So, rather than So, is used for
standard entropies to emphasize that they
originate from the third law.

Entropy Change for a Reaction
You can calculate the entropy change for

a reaction using a summation law, similar to
the way you obtained Ho.
S   nS (products)   mS (reactants)
o o o
Even without knowing the values for the

entropies of substances, you can sometimes
predict the sign of So for a reaction.


The entropy usually increases in the following
situations:
1. A reaction in which a molecule is broken
into two or more smaller molecules.


situations:
2. A reaction in which there is an increase in
the moles of gases.


situations:
3. A process in which a solid changes to
liquid or gas or a liquid changes to gas.

Calculate the change in entropy, So, at 25 oC for the

reaction in which urea is formed from NH3 and CO2.
The standard entropy of NH2CONH2 is 174 J/(mol.K).
See Table in handbook for other values.
2NH 3 (g )  CO 2 (g )  NH 2CONH2 (aq)  H 2O(l )
The calculation is similar to that used to obtain
Ho from standard enthalpies of formation.


See Table 19.1 for other values.
So: 2 x 193 214 174 70
It is convenient to put the standard entropies
(multiplied by their stoichiometric
coefficients) below the formulas.


We can now use the summation law to
calculate the entropy change.
So   nSo (products)   mSo (reactants)


We can now use the summation law to
calculate the entropy change.
So  [(174  70)  ( 2  193  214)]J / K  356 J/K

Free Energy Concept
The American physicist J. Willard Gibbs

introduced the concept of free energy
(sometimes called the Gibbs free energy), G,
which is a thermodynamic quantity defined by
the equation G=H-TS.
This quantity gives a direct criterion for
spontaneity of reaction.

Free Energy and Spontaneity
Changes in H an S during a reaction result

in a change in free energy, G , given by
the equation
 G   H  T S
Thus, if you can show that G is negative at a
given temperature and pressure, you can predict
that the reaction will be spontaneous.

Standard Free-Energy Change
The standard free energy change, Go, is

the free energy change that occurs when
reactants and products are in their standard
states.
The next example illustrates the calculation of
the standard free energy change, Go, from Ho
and So.
o o o
 G   H  T S
What is the standard free energy change, Go , for

the following reaction at 25 oC? Use values of
Hfo and So, from Tables 6.2 and 19.1.
N 2 (g )  3H 2 (g )  2NH 3 (g )
Hfo: 0 0 2 x (-45.9) kJ
So: 191.5 3 x 130.6 2 x 193 J/K
Place below each formula the values of Hfo

and So multiplied by stoichiometric coefficients.


N 2 (g )  3H 2 (g )  2NH 3 (g )
You can calculate Ho and So using their
respective summation laws.
H   o o
nH f (products)   o
mH f (reactants)
 [2  ( 45.9)  0] kJ  91.8 kJ

N 2 (g )  3H 2 (g )  2NH 3 (g )

o o o
 [2  193  (191.5  3  130.6)] J/K  -197 J/K


N 2 (g )  3H 2 (g )  2NH 3 (g )
Now substitute into our equation for Go. Note
that So is converted to kJ/K.
 G o   H o  T S o
 91.8 kJ  (298 K)( 0.197 kJ/K)
 33.1 kJ
Standard Free Energies of
Formation
The standard free energy of formation, Gfo,
of a substance is the free energy change that
occurs when 1 mol of a substance is formed
from its elements in their stablest states at 1 atm
pressure and 25 oC.
By tabulating Gfo for substances, as in Table
in Handbook, you can calculate the Go for a
reaction by using a summation law.
G o   nG of (products)   mG of (reactants)
Calculate Go for the combustion of 1 mol of

ethanol, C2H5OH, at 25 oC. Use the standard free
energies of formation given in Table (Handbook).
C2 H 5OH(l )  3O 2 (g )  2CO 2 (g )  3H 2O(g )
Gfo: -174.8 0 2(-394.4) 3(-228.6)kJ
Place below each formula the values of Gfo
multiplied by stoichiometric coefficients.


energies of formation given in Table 19.2.
C2 H 5OH(l )  3O 2 (g )  2CO 2 (g )  3H 2O(g )
Gfo: -174.8 0 2(-394.4) 3(-228.6)kJ
You can calculate Go using the summation
law.
G o  [2( 394.4)  3( 228.6)  ( 174.8)] kJ

energies of formation given in Table 19.2.
C2 H 5OH(l )  3O 2 (g )  2CO 2 (g )  3H 2O(g )
Gfo: -174.8 0 2(-394.4) 3(-228.6)kJ
You can calculate Go using the summation
law.
G o  1299.8 kJ
G as a Criteria for Spontaneity
o
The following rules are useful in judging

the spontaneity of a reaction.
1. When Go is a large negative number (more
negative than about –10 kJ), the reaction is
spontaneous as written, and the reactants
transform almost entirely to products when
equilibrium is reached.

o

2. When Go is a large positive number (more
positive than about +10 kJ), the reaction is
nonspontaneous as written, and reactants do
not give significant amounts of product at
equilibrium.

o

3. When Go is a small negative or positive
value (less than about 10 kJ), the reaction
gives an equilibrium mixture with
significant amounts of both reactants and
products.

Maximum Work
Often reactions are not carried out in a way

that does useful work.
As a spontaneous precipitation reaction occurs,
the free energy of the system decreases and
entropy is produced, but no useful work is
obtained.
In principle, if a reaction is carried out to obtain
the maximum useful work, no entropy is
produced.

Maximum Work
Often reactions are not carried out in a way

that does useful work.
It can be shown that the maximum useful work,
wmax , for a spontaneous reaction is G.
wmax  G
The term free energy comes from this result.

Free Energy Change During
Reaction
As a system approaches equilibrium, the
instantaneous change in free energy
approaches zero.
Figure 1. illustrates the change in free energy
during a spontaneous reaction.
As the reaction proceeds, the free energy
eventually reaches its minimum value.
At that point, G = 0, and the net reaction
stops; it comes to equilibrium.
Figure 1. Free-energy change during a spontaneous reaction.
Free Energy Change During
Reaction
As a system approaches equilibrium, the
instantaneous change in free energy
approaches zero.
Figure 1 illustrates the change in free energy
during a nonspontaneous reaction.
Note that there is a small decrease in free
energy as the system goes to equilibrium.

Figure 2 Free-energy change during a nonspontaneous reaction.
Relating Go to the Equilibrium
Constant
The free energy change when reactants are
in non-standard states (other than 1 atm
pressure or 1 M) is related to the standard
free energy change, Go, by the following
equation.
o
G  G  RT ln Q
Here Q is the thermodynamic form of the
reaction quotient.

Constant
equation.
o
G represents an instantaneous change in free
energy at some point in the reaction
approaching equilibrium.
Constant
equation.
o
At equilibrium, G=0 and the reaction quotient
Q becomes the equilibrium constant K.

Constant
equation.
o
0  G  RT ln K
At equilibrium, G=0 and the reaction quotient
Q becomes the equilibrium constant K.

Constant
This result easily rearranges to give the basic
equation relating the standard free-energy
change to the equilibrium constant.
o
G   RT ln K
When K > 1 , the ln K is positive and Go is
negative.
When K < 1 , the ln K is negative and Go is
positive.

Find the value for the equilibrium constant, K, at 25 oC

(298 K) for the following reaction. The standard free-
energy change, Go, at 25 oC equals –13.6 kJ.
2NH 3 (g )  CO 2 (g ) NH 2CONH 2 (aq)  H 2O(l )
Rearrange the equation Go=-RTlnK to give

o
G
ln K 
 RT


Substituting numerical values into the equation,

3
 13.6  10 J
ln K   5.49
 8.31 J/(mol  K)  298 K


Hence,
5.49 2
K e  2.42  10

Spontaneity and Temperature
Change
All of the four possible choices of signs for
Ho and So give different temperature
behaviors for Go.
Ho So Go Description
– – – Spontaneous at all T
+ + + Nonspontaneous at all T
– – + or – Spontaneous at low T;
Nonspontaneous at high T
+ + + or – Nonspontaneous at low T;
Spontaneous at high T
Calculation of Go at Various
Temperatures
In this method you assume that Ho and So
are essentially constant with respect to
temperature.
You get the value of GTo at any temperature T
by substituting values of Ho and So at 25 oC
into the following equation.
o o o
G T   H  T S

Find the Go for the following reaction at 25 oC

and 1000 oC. Relate this to reaction spontaneity.
CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
Place below each formula the values of Hfo

and So multiplied by stoichiometric coefficients.


CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K


CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
H   o o
nH f (products)   o
mH f (reactants)
 [( 635.1  393.5)  ( 1206.9)]kJ  178.3 kJ


CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K

o o o
 [( 38.2  213.7 )  (92.9)]  159.0 J / K


CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
Now you substitute Ho, So (=0.1590 kJ/K),
and T (=298K) into the equation for Gfo.
o o o
G T   H  T S

CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
o
G T  178.3kJ  ( 298 K )(0.1590 kJ / K )

CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
o So the reaction is
G T  130.9 kJ nonspontaneous
at 25 oC.

CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
Now we’ll use 1000 oC (1273 K) along with
our previous values for Ho and So.
o
G T  178.3kJ  (1273 K )(0.1590 kJ / K )

CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
Now we’ll use 1000 oC (1273 K) along with
our previous values for Ho and So.
o So the reaction is
G T  24.1 kJ spontaneous at
1000 oC.

CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
To determine the minimum temperature for
spontaneity, we can set Gfo =0 and solve for T.
o
H
T o
S

CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
To determine the minimum temperature for
spontaneity, we can set Gfo =0 and solve for T.
178.3 kJ o
T  1121 K (848 C)
0.1590 kJ / K

CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ
So : 92.9 38.2 213.7 J/K
Thus, CaCO3 should be thermally stable until
its heated to approximately 848 oC.

Operational Skills
Calculating the entropy change for a phase transition
Predicting the sign of the entropy change of a reaction
Calculating So for a reaction
Calculating Go from Ho and So
Calculating Go from standard free energies of formation
Interpreting the sign of Go
Writing the expression for a thermodynamic equilibrium
constant
Calculating K from the standard free energy change
Calculating Go and K at various temperatures

Figure 3. Examples of a
spontaneous and nonspontaneous
process.
Return to slide 21

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Thermodynamics

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Thermodynamics is the study of the

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 2

To state the laws of thermodynamics, we

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 3

To state the laws of thermodynamics, we

To state the laws of thermodynamics, we

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 5

To state the laws of thermodynamics, we

To state the laws of thermodynamics, we

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 7

To state the laws of thermodynamics, we

The system gains internal energy from the heat

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 8

To state the laws of thermodynamics, we

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 9

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 11

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 12

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 13

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 14

In this lecture, we tentatively defined

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 17

In this lecture, we tentatively defined

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 18

In this lecture, we tentatively defined

Chapter 19 Copyright © by Houghton Mifflin Company. All rights reserved. 19

In this lecture, we tentatively defined

H o   nH of (products)   mH of (reactants)

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The heat of vaporization, Hvap of carbon

The heat of vaporization, Hvap of carbon

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This inequality implies that for a reaction to be

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You can calculate the entropy change for

Even without knowing the values for the

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You can calculate the entropy change for

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You can calculate the entropy change for

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You can calculate the entropy change for

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Calculate the change in entropy, So, at 25 oC for the

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Calculate the change in entropy, So, at 25 oC for the

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Calculate the change in entropy, So, at 25 oC for the

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Calculate the change in entropy, So, at 25 oC for the

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The American physicist J. Willard Gibbs