Chapter 15b Thermodynamics sp08 PDF

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1
Chapter 15b
Thermodynamics: The First Law
2
Work and Energy
Work motion against an opposing force.
A weight raised against the pull of gravity.
A chemical reaction in a battery pushes an electric
current through a circuit.
The work required to move an object a certain distance
against an opposing force is calculated:
Work = force distance
Work = energy = joules
1J = 1 kgm
2
s
2
3
Work and Energy
The capacity of a system to do work is called internal
energy (E) also (U).
Internal energy is its total store of energy
The internal energy of a substance represents all the
energy contained within the substance that includes:
Kinetic energy of the molecules
Energies of attraction and repulsion among subatomic
particles, atoms, ions or molecules.
It is the sum of the kinetic and potential energies of all
the particles in the system.
4
Work and Energy
The absolute value of internal energy of a system cannot
be measured.
Instead, the change in internal energy is measured.
X means a change in (a difference in) the property of X.
X = X
final
X
initial
A negative value of X indicates that the value of X has
decreased during a change.
A positive value of X indicates that the value of X has
increased during a change.
5
Work and Energy
When work is done on a system, the internal energy
is increased.
Compressing a gas inside a thermally insulated
container increases the internal energy of the gas.
The hot compressed gas can do more work than a cooler
gas that is not compressed.
Passing an electric current through a system, such as
charging a battery, increases the batterys capacity to
do work.
6
If X = E:
E is negative; then the system has used up some of the
stored energy
E is positive; then the system has increased it stored
energy
Lowest point of potential
(stored) energy. E is
negative
Highest point of potential
(stored) energy. E is positive
Winding a spring increases the potential energy
2
7
Work and Energy
As indicated by the text, we always take the
systems point of view.
If work is done on the system, the internal energy of
the system increases.
Increasing internal energy would have a positive value.
If work is done by the system, the internal energy of
the system decreases.
Decreasing internal energy would have a negative
value.
8
Work and Energy
The symbol w is used to denote the energy transferred to
a system by doing work.
E = w
If energy is transferred to a system as work, the internal
energy of the system increases and w is positive
E.g., compressing a gas in an insulated container
If energy leaves the system as work, the internal energy
of the system decreases and w is negative.
E.g., allowing the gas to expand again.
9
Expansion Work
A system can do two kinds of work: Expansion or Nonexpansion.
1. Expansion work the work of expansion against an
external force.
E.g., a gas expanding in a cylinder fitted with a piston
the expanding gas must push against the piston that must
in turn push against the pressure of the atmosphere.
The work done by an expanding gas can be described by
the following relationship at constant external pressure.
w = P
ex
V
w = P
ex
(V
2
V
1
)
This equation is applicable only to systems in which the
external pressure is constant during expansion.
10
Figure 9.4: The piston moving a
distance
( )
Work force distance
distance h the distance the piston moves
Work force h
=
=
=
F
P rearranging F P A
A
F force
A area
= =
=
=
: Substituting F in the work equation with P A
Work P A h
Volume of a cylinder A h
V A h
Work P V
=
=
=
=
11
Work and Energy
The work expression describes the magnitude of work to
expand a gas by the change in volume against a pressure.
When a gas expands against a pressure, then the system is
doing work on the surroundings.
The system is losing internal energy in the form of work.
The sign of work is negative.
The V is increasing and is positive.
Since work must be negative when the internal energy of the
system decreases, the work equation becomes:
w P V =
w P V =
12
The external
pressure ,
atmospheric
pressure, is the
force opposing
expansion.
The piston is held
in place by an
external pressure.
The piston is
released and the
gas expands.
When a system
expands, it loses
energy as work.
When the V is
positive, w is
negative.
3
13
Work and Energy
If the external pressure is expressed in SI units of
Pascal's and change in volume is expressed in m
3
.
( ) ( ) ( )
1 2
2
3 3
2 2
1 1
1 1
1 1
Pa kg m s
kg kg m
Pa m m joule
m s s

=
| |
= = =
|
\ .
14
Work and Energy
If the pressure is expressed in atmospheres and
the volume is in liters:
joule m Pa
m Pa
atm
Pa
cm
m
L
cm
atm L
325 . 101 325 . 101
325 . 101
1
10 325 . 101
10
1 10
1
3
3
3
3 6
3 3 3
=
=
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
15
Work and Energy
2. Nonexpansion work involves work that does not
involve a change in volume.
A chemical reaction can do nonexpansion work by
causing an electrical current to flow.
16
Work and Energy
Free expansion describes a system in which
expansion occurs without work being done.
If the system is in a vacuum, the external energy is
zero.
A system does no expansion work when it expands into
a vacuum because there is no opposing force.
17
Heat
The internal energy within a system can also be
changed by transferring energy in the form of heat
into or out of the surroundings.
In thermodynamics:
Heat is energy that is transferred as a result of a
temperature difference.
Temperature is a property that is a result of the random
motions of the particles in a particular substance.
Energy flows as heat from a region of high-temperature
to a region of lower-temperature.
18
Heat
In an system that is not insulated:
If the system is cooler than its surroundings, then
energy will flow into the system from its surroundings.
Increasing energy causes the molecules in the system to
move more vigorously.
The more kinetic molecules in the system causes the
internal energy of the system to increase.
Increasing the internal energy increases the
temperature.
4
19
Heat
Energy that is transferred as heat (q) is measured in
joules.
cal = 4.184 J
Cal = 1kcal = 4.184 x 10
3
J
(Cal is the nutritional calorie)
The sign of q represents whether heat has entered or
left the system.
20
Heat
q 0 if heat is absorbed by the system.
q 0 if heat is released by the system.
>
<
If heat enters the system and the only outcome is a
change of temperature but no work is done, then q = E
When heat energy is released from the system into the
surroundings, the internal energy of the system
decreases, E < 0
When heat energy is absorbed into the system from the
surroundings, the internal energy of the system increases,
E > 0
21
Surroundings
22
Heat
Exothermic processes: heat is released into the
surroundings.
Almost all chemical reactions and all combustion
reactions are exothermic.
Endothermic processes: heat is absorbed from the
surroundings.
melting
Vaporization
Some chemical reactions
23
Figure 9.2: Combustion of methane
releases the quantity of energy
CH
4
(g) + 2O
2 (g)
CO
2
(g) + 2H
2
O (g) + heat
E; the internal energy of
the system has decreased
Exothermic process
24
Figure 9.3: Energy diagram for the
reaction of nitrogen and oxygen
N
2
(g) + O
2
(g) + heat 2NO (g)
+ E; the internal energy of
the system has increased
Endothermic process
5
25
NH
4
SCN plus
Ba(OH)
2
8H
2
O is an
endothermic reaction
that causes
atmospheric H
2
O
vapor to freeze on the
outside of the beaker.
26
Internal Energy
The First Law of Thermodynamics states, The
combined amount of energy in the universe is
constant.
The first law is also known as the Law of
Conservation of Energy.
Energy is neither created nor destroyed in chemical
reactions and physical changes.
27
Internal Energy
The internal energy, E, is all of the energy contained
within a substance.
The First Law of Thermodynamics states that the
change in internal energy, (E), is determined by the
heat flow, q, and the work, w.
E = q + w
28
p.605
29
Changes in Internal Energy
Example: If 1200 joules of heat are added to a
system in energy state E
1
, and the system does
800 joules of work on the surroundings, what is
the :
1. The energy change for the system, E
sys
?
E = E - E = q + w
E =1200 J + (-800 J)
E = 400 J
E = + 400 J
2 1
sys
30
2. The energy change of the surroundings,
E
surr
?
E J
surr
= 400
3. The energy of the system in the new state, E
2
?
E E - E
E E E
E J
sys 2 1
2 1 sys
1
=
= +
= + 400
6
31
According to the first law, any change in the internal
energy of the system must arise from the transfer of
heat energy between the system and its surroundings.
At constant volume:
E = q
If the dry ice absorbed 1300 J of heat energy from the
surroundings, then q = +1300 J.
If E = q, then E = + 1300 J
32
In most chemical and physical changes, the only kind of
work is pressure-volume work.
E.g. A system that absorbs heat and does work.
As the dry ice absorbs heat from the
surroundings, some solid CO
2
sublimes to form gaseous CO
2.
The
larger volume of gas causes the bag to
expand. The expanding gas does the
work of raising a book that has been
placed on the bag.
Some powdered dry ice
(solid CO
2
) is placed into a
flexible bag, which is then
sealed.
33
The work done on a system or by a system depends on the
external pressure and the volume.
When the external pressure is constant during a change,
the amount of work done is equal to this pressure times
the change in volume.
w = PV or w = P (V
2
V
1
)
34
Pressure is force per
unit area.
Volume is distance
cubed.
P =
force
area
F
d
2
=
V = d
3
( )
P V =
F
d
d F d which is work
2
3
|
\
|
.
| =
PV is a work term, i.e., the same units are used for
energy and work.
35
In constant-volume reactions, no PV is done.
The volume does not change.
If heat evolved or was absorbed during the change,
the change in internal energy of the system is just
the amount of heat released or absorbed at constant
volume.
E = q - PV
E = q
36
E.g. (A closed system) Some dry ice is placed into a rigid flask,
which is then sealed.
As the dry ice absorbs heat from the surroundings, some of the
dry ice sublimes to form carbon dioxide gas.
2 2
( ) ( )
heat
CO s CO g
A gas is produced but the
system cannot do work by
expanding the walls are too
rigid, the volume is constant.
A system maintained at
constant volume can do no
expansion work.
Although the pressure within the vessel increases, there is no
expansion (V =0).
PV = 0 ; therefore, no work is done. E = q
7
37
When a gas is produced against constant external
pressure, such as in an open vessel at atmospheric
pressure:
the gas does work as it expands against the pressure of the
atmosphere.
If no heat is absorbed during the expansion:
The result is a decrease in the internal energy of the system.
When a gas is consumed in a process against constant
external pressure:
The atmosphere does work on the reacting system.
38
For example: the complete reaction of a 2:1 mole ratio
of H
2
and O
2
gases to produce steam at some constant
temperature above 100
o
C and at 1.0 atm.
2 H
2
(g) + O
2
(g) 2 H
2
O (g)
39
Fig. 15-7, p.606
2 H
2
(g) + O
2
(g) 2 H
2
O (g)
Assume that the constant-temperature bath surrounding the
reaction vessel completely absorbs all the evolved heat so that the
temperature of the gases does not change.
The volume of the system
decreases by one third.
The surroundings exert a
constant pressure of 1.0
atm and do work on the
system by compressing it.
The internal energy of the
system increases by an
amount equal to the amount
of work done on it.
3 mol gases 2 mol gases
40
Using the ideal gas law PV = nRT, we can look at
volume changes of ideal gases at constant T and P
due to changes in the number of moles of gas present,
n
gas
.
( ) ( )
PV = nRT
P V n RT
gas
=
n
gas
= (number of moles of gaseous products)
(number of moles of gaseous reactants)
41
Work is defined as a force acting through a specified
distance.
( )
( )
gas
gas
Thus we can see
w F d
P V
n RT
n that
at constant T and P
RT
.
w
=
=
=
=
Consequently, there are three possibilities for volume
changes:
42
When Then Examples
V
1
V
2

gas mol 2
2(g) (g) 2
gas mol 2
(g) 2 (g)
CO H O H CO + +
2. V
2
> V
1
PV > 0
n
gas
> 0
1. V
2
= V
1
PV = 0
n
gas
= 0

gas mol 1
2(g) 2(aq)
gas mol 0
(aq) (s)
H ZnCl HCl 2 Zn + +

gas mol 2
3(g)
gas mol 4
2(g) 2(g)
NH 2 H 3 N +
3. V
2
< V
1
PV < 0
n
gas
< 0
8
43
Consider the following gas phase reaction at
constant pressure at 200
o
C.
( ) ( ) ( )
2 NO + O 2 NO
g 2 g
3 mol gas
2 g
2 mol gas

2 1
The reaction produces less moles of gas than in the original reactants.
The constant pressure exerted by the atmosphere decreased the volume.
Con
V V thus V 0 and P V 0.
sequently, w P V 0.
Work
<
>
<
=
<
is done on system by surroundings.

44
Consider the following gas phase reaction at constant
pressure at 1000
o
C.
( ) ( ) ( )

gas mol 2
g 2 g 3
gas mol 1
g 5
Cl PCl PCl +
2 1
The increase in volume was a result of more moles of gas products than reactants.
The increase of gas products increases volume against constant pres
V V thus
sure.
Co
V 0 and P V
nsequently,
.

0
w
> >
=
>
P V 0.
Work is done by the system on the surrounding .
.
s The internal energy of the system
decreases by the amount of work done by the system
<
45
Enthalpy
The fundamental definition of enthalpy, H, is
H = E + PV
The change of enthalpy, H, is the quantity of heat transferred
into or out of a system as it undergoes a chemical or physical
change at constant temperature and pressure.
An enthalpy change is sometimes loosely referred to as a heat
change or heat of a reaction.
The enthalpy change is equal to the enthalpy or heat content of
the substances produced minus the enthalpy of the substances
consumed.
H = H
final
H
initial
H = H
substances produced
H
substances consumed
46
Relationship of H and E
The total amount of heat energy that a system can
provide to its surroundings at constant temperature
and pressure is given by
H = E + P V
which is the relationship between H and E.
H = change in enthalpy of system
E = change in internal energy of system
PV = work done by system
47
We defined enthalpy as H = q
P
. (q
p
= constant
pressure)
We also define H = E + PV.
Are these two definitions compatible?
Remember E = q + w.
We have also defined w = PV .
Thus E = q + w
= q PV
Consequently, H = (q PV) + (PV) = q
At constant pressure H = q
P
.
48
For reactions in which the volume change is very
small or equal to zero.
E. H
change, volume no For
E. H
then V P E H Since
0. V P and 0 V
changes, volume small For
=

+ =

9
49
E is negative when energy is released by a system
undergoing a chemical or physical change at constant
pressure and constant volume.
Energy can be written as a product of the process.
3
5 12 2(g) 2(g) 2 ( ) ( )
C H 8 O 5 CO 6 H O 3.516 10 kJ + + +

Indicates the
release of energy
3
3
H 3.516 10 kJ
-or-
E 3.516 10 kJ
=
=
50
E is positive when energy is absorbed by a system
undergoing a chemical or physical change at constant
pressure and constant volume.
Energy can be written as a reactant of the process.
3
2(g) 2 ( ) 5 12 2(g) ( )
5 CO 6 HO 3.516 10 kJ CH 8 O + + +

Indicates the
absorption of energy
3
3
H = 3.516 10 kJ
-or-
E 3.516 10 kJ
+
= +
51
When heat energy has been transferred to a constant-
pressure system, the enthalpy of the system increases by
that amount.
When heat energy has been released from constant-
pressure system, the enthalpy of the system decreases by
that amount.
E.g., the formation of zinc iodide from its elements
is an exothermic reaction that releases 208 kJ of
heat to the surroundings for each mole of zinc
iodide formed at constant pressure.
Zn (s) + I
2
(s) ZnI
2
(s)
52
Change in enthalpy, H, or heat of reaction is
amount of heat absorbed or released when a reaction
occurs at constant pressure.
The change in energy, E, is the amount of heat
absorbed or released when a reaction occurs at
constant volume.
How much do the H and E for a reaction differ?
The difference depends on the amount of work performed
by the system or the surroundings.
53
The enthalpy of the system is
like a measure of water in a
reservoir. When the reaction
releases 208 kJ of heat at
constant pressure, the reservoir
falls by 208 kJ and the H =
208kJ
When the reaction absorbs
208 kJ of heat at constant
pressure, the reservoir rises
by 208 kJ and the H =
+208kJ
54
Example: Given that the combustion of n-pentane, n-
C
5
H
12
, at constant pressure releases 3523 kJ of heat at
a temperature of 298K.
,
H = -3523 kJ/mol
What are the values of the work term and E for this
reaction?
) ( 2 2(g) 2(g) ) 12( 5
O H 6 CO 5 O 8 H C

+ +
8 mol of gas 5 mol of gas
10
55
Determine the work done by this reaction.
5 12( ) 2(g) 2(g) 2 ( )
8 mol gas 5 mol gas
gas
gas
J
mol K
C H 8 O 5 CO 6 H O
H -3523 kJ/mol, T 298 K.
w -P V -( n )RT
n 5 8 mol -3 mol
w -(-3 mol)(8.314 )(298 K) 7433 J 7.433 kJ
wor
+ +
= =
= =
= =
= = =

k is done on the system by the surroundings
56
Now calculate the E for this reaction from the values
of H and w that we have determined.
Remember, work is done on the system by the surroundings;
therefore, work is positive.
( ) ( )
3523
7.422
3523 7.422
3516
E q w
H kJ
w kJ
E kJ kJ
kJ
= +
=
= +
= + +
=
57
Example: Assuming the gases are ideal, calculate the
amount of work done, in joules, for the conversion of
1.00 mole of Ni to Ni(CO)
4
at 75C in the reaction
below. The value of R is 8.314 J/molK.
Ni(s) + 4CO(g) Ni(CO)
4
(g)
We will calculate this one in class.
58
The reaction of 1.00 mole of H
2
(g) with 0.500 mole
of O
2
(g) to produce 1.00 mole of steam, H
2
O(g), at
100C and 1.00 atm pressure evolves 242 kJ of heat.
Calculate E per mole of H
2
O(g) produced. The
universal gas constant is 8.314 J/molK.
We will calculate this problem in class.
59
Spontaneous Changes
Spontaneous changes happen without any continuing
outside influences.
A spontaneous change has a natural direction.
For example the rusting of iron occurs spontaneously.
Have you ever seen rust turn into iron metal without
man made interference?
The melting of ice at room temperature occurs
spontaneously.
Will water spontaneously freeze at room temperature?
60
Spontaneous Changes
A spontaneous change in a process has a natural
tendency to occur.
The change does not necessarily occur rapidly
A nonspontaneous change in a process can be brought
about only by doing work.
11
61
Entropy and Disorder
Observations of such events as:
A hot block of metal cools as the energy of its
vigorous vibrating atoms spreads into the
surroundings
It is highly improvable that energy will gather from the
surroundings and concentrate in a small block of metal
The randomly moving molecules of a gas spread
throughout their containers
It is highly improvable that the random motion of gases
will bring them all simultaneously back into one corner of
the container.
62
The common characteristic that causes processes to
spontaneous in only one direction comes from many
years of observations.
The increase in a property called entropy appears to
responsible for spontaneity in processes.
The change in the entropy of the universe for a given
process is a measure of the driving force behind that
process.
63
Energy and matter tend to become more disordered.
In thermodynamics, this idea of a tendency toward
disorder is call entropy (S).
High disorder represents high entropy.
Low disorder represents low entropy.
64
Entropy is closely associated with the probability that
the more ways a particular state can be achieved, the
greater the probability that that state will occur.
Nature tends to spontaneously proceed to a state which
has the highest probability of existence.
65
Figure 10.3: Expansion of an ideal gas into an evacuated
bulb
Gases are
distributed
evenly when
allowed to
expand into an
evacuated bulb.
66
Figure 10.4: Three possible arrangements
(states) of four molecules.
12
67
Arrangement I only one
possible arrangement, all
the molecules must be at
one end of the two-
bulbed flask.
Arrangement II four
possible arrangements.
Arrangement III six
possible arrangements.
The probability of a particular state occurring depends on the number of ways in
which the microstate can be achieved.
68
If there are two
molecules in the two-
bulbed flask, there is one
chance in four that both
molecules will be in the
left bulb.
If a system has several available states, the one state that has the
greatest number of microstates is the one that is most likely to occur.
69
The Second Law of Thermodynamics
The second law of thermodynamics states, In
spontaneous changes the universe tends towards
a state of greater disorder.
Spontaneous processes have two requirements:
1. The free energy change of the system must be
negative.
2. The entropy (disorder) of the universe must
increase.
Fundamentally, the system must be capable of
doing useful work on surroundings for a
spontaneous process to occur.
70
Changes in Entropy
The entropy of an isolated system increases during
the course of a spontaneous change.
E.g. As a hot block of metal cools, the entropy
increases as energy spreads into the surroundings.
The isolated system (the universe) is the hot block of
metal and its immediate surroundings.
During the expansion of a gas the entropy is
increased as the molecules spread through the
container.
71
Changes in Entropy
Provided that the temperature is constant, the change in
the entropy of a system can be calculated from the
following expression:
Where q
rev
signifies that the energy must be transferred
reversibily (through an infinite number of steps).
For a reversible transfer of energy as heat, the
temperatures of the surroundings and the system
must be only infinitesimally different.
T
q
S
rev
=
72
Changes in Entropy
Example:
a) Calculate the change in entropy in 1.0 L of water at
0.
o
C when it absorbs 235 J of energy from a heater.
b) If the 1.0 L of water is at 99
o
C, what is the change in
entropy?
c) Explain any difference in entropy change.
13
73
K
J 632 . 0
K 372
J 235
T
H
T
q
S
K 372 273 99 C 99 ) b
K
J 861 . 0
K 273
J 235
T
H
T
q
S
J 235 H
K 273 273 0 . 0 C 0 . 0 ) a
rev
o
rev
o
= =
= =
= + =
= =
= =
=
= + =
c) The change in entropy is smaller for the water at higher
temperatures because the water molecules are already more
chaotic.
At lower temperatures, the same amount of heat transferred to
the water had a greater effect on changes in entropy.
Heat added to system is
endothermic.
74
Changes in Entropy
The disorder of a system is expected to increase when heat is
added because the additional heat energy increases the thermal
motion of the molecules.
Heating increases the thermal disorder.
The disorder of a system is expected to increase when a given
amount of matter spreads into a greater volume or is mixed
with another substance.
Spreading the molecules of a substance into additional
locations increases the positional disorder.
75
Changes in Entropy
Example: A sample of 0.0410 mol of N
2
gas is
heated from 20.0
o
C to 400.
o
C at constant volume.
What is the change in the entropy of the nitrogen?
The molar heat capacity of nitrogen at constant
volume is 20.81 J/mol K. Assume ideal behavior.
76
Changes in Entropy
Increasing thermal disorder increases the ranges of
different energies that the molecules can have.
Sometimes spontaneous changes are accompanied by
a change in volume.
The larger volume provides more locations for the
molecules and increases positional disorder.
An increase in positional disorder increases the entropy
of the system.
77
Entropy, S
Entropy is a measure of the disorder or randomness
of a system.
As with H, entropies have been measured and
tabulated in Appendix four as S
o
298
When:
S > 0 disorder increases (which favors spontaneity).
S < 0 disorder decreases (does not favor
spontaneity).
78
Entropy, S, of Changing Physical States
During physical changes:
The entropy increases when a solid melts and its
molecules become more disordered.
The entropy increases even more when a liquid
vaporizes because its molecules occupy a much greater
volume and their motion is highly chaotic.
14
79
80
Entropy, S
From the Second Law of Thermodynamics, for a spontaneous
process to occur:
In general for a substance in its three states of matter:
S
gas
> S
liquid
> S
solid
0 S S S
gs surroundin system universe
> + =
81
To determine the change in entropy for a
substance undergoing a physical change at its
transition temperature (vaporization or melting)
three important facts should be noted:
1. At the transition temperature, the temperature of
the substance remains constant as heat is
supplied.
E.g., the temperature remains at 100.0
o
C (at 1.0
atm) when water is vaporized from a liquid to a
gas.
82
2. At the temperature of a phase transition, the
transfer of heat is reversible.
If the temperature is fixed at 1.0 atm, raising the
temperature of the surroundings by an
infinitesimal (very small) amount results in the
complete vaporization, and lowering the
temperature causes complete condensation.
3. As a result of the transition occurring at constant
pressure, the heat added is equal to the change in
enthalpy of the substance.
83
The entropy of vaporization is the change in
entropy per mole of molecules when a
substance changes from a liquid into a vapor.
The heat required per mole to vaporize the
liquid at constant pressure is equal to the
enthalpy of the vaporization, H
vap.
(q
rev
= H
vap
)
The entropy of vaporization at the normal
boiling point is
b
vap
T
H
S

=
84
When a liquid and its vapor are in their standard
states (both are pure and at 1.00 atm or bar) the
standard entropy of vaporization is:
All standard entropies of vaporization are
positive (becoming more disorganized) and are,
therefore; reported without their positive signs.
o
vap
S
15
85
86
A smaller increase in entropy occurs when solids
melt because a liquid is only slightly more
disordered than a solid.
Therefore, the standard entropy of fusion of a
substance at its melting point i:.
o
fus
fus
f
H
S
T
=
87
Example: Calculate the entropy change for:
a) The vaporization of 1.00 mol of H
2
O
(l)
at 100.
o
C.
b) The freezing of 3.33 g of C
2
H
5
OH at 158.7K. The
H
fus
= 4.60 kJ/mol K
a)
mol K
J
K
mol J
T
H
T
q
S
mol K
J
are S of units The
K T
mol
kJ
H
vap
= =
= =
= + = =
109
373
/ 40700
373 273 . 100 ; 7 . 40
88
( )
( )
2 5
2 5
2 5 2 5
2 5
)
4600 J
C H OH
mol
4600 J/mol 28.99
158.7 K
1.0 C H OH 28.99
3.33 g C H OH 2.09 C H OH
46.07 g C H OH
fus
fus
b
H for
H q J
S
T T K mol
mol J J
K mol K
=
| |
= = = =
|

\ .
| |
| |
=
| |
\ .
\ .
The freezing of 3.33 g of C
2
H
5
OH at 158.7K. H
fus
= 4.60 kJ/mol K
89
Entropy, S
The Third Law of Thermodynamics states, The
entropy of a pure, perfect, crystalline solid at 0 K is
zero.
This law permits us to measure the absolute values of
the entropy for substances.
To get the actual value of S, cool a substance to 0 K,
or as close as possible, then measure the entropy
increase as the substance heats from 0 to higher
temperatures.
Notice that the Appendix has values of S not S.
90
Molecular Interpretation of Entropy
The entropies of all perfect crystals approach zero as
the absolute temperature approaches zero.
The perfect crystal refers to a substance in which all the
atoms are in a perfectly orderly array, which means
there is no positional disorder
there is no thermal disorder
16
91
When measuring a sample of molecules at a
temperature close to T = 0, the entropy of the sample
depends upon the residual entropy that survives at
that temperature.
The residual entropy is determined by the number of
orientations a sample (usually a mole) of molecules
may have in a crystal.
92
E.g. A sample of CO molecules at a temperature
close to T=0 has a residual entropy of 4.6 JK
1
.
This occurs from the different orientations that a
sample of CO molecules may take when forming a
crystal.
The different orientations of CO molecules in the
crystal cause some positional disorder, and therefore;
the S is greater than zero.
93
Possible orientations of 4 CO molecules in a crystal.
If the molecules in the crystal where all in the same orientation,
head to head, or tail to tail, the entropy of the system would be zero.
However, the dipole moments of CO molecules are very small and
as a result, the molecules are able to arrange randomly in one of 16
orientations.
4 CO molecule have 2
4
possible arrangements in a
crystal.
Since the crystal is not a
perfectly ordered array,
some positional disorder is
seen in the crystal-called
residual entropy.
94
A sample of HCl molecules have an entropy (S) very
close to zero at a temperature close to T= 0.
The dipole moments of HCl molecules are much
greater than CO molecules and orientate the
molecules in a head to head or tail to tail
arrangement.
As a result, there is no positional disorder and S 0.
95
Standard Molar Entropies
The standard molar entropies of gases are higher than
those of comparable solids and liquids at the same
temperature.
Liquids have higher molar entropies than solids
because of the greater freedom of movement of the
molecules.
Gases that occupy greater volumes have higher molar
entropies than gases in lower volumes at the same
temperature.
96
Standard Molar Entropies
17
97
Standard Reaction Entropies
Entropy is useful as a predictor of the natural
direction of a reaction.
The entropy of the reaction system (reactants forming
products) changes.
The heat released or absorbed during the process of the
reaction also affects the entropy of the surroundings.
98
Often, we can predict the sign of the entropy
change of a system without calculations.
A change in the amount of gas molecules either
used up or produced during a reaction normally
dominates any other entropy change in a reaction.
A net increase in the amount of gas usually
results in a +S.
A net consumption in the amount of gas usually
results in a S.
99
Changes in a system that predict an increase in
entropy also include:
A liquid to gas usually results in a +S.
A solid to a liquid usually results in a +S.
A solid to a gas usually results in a +S.
A solid dissolved in a liquid usually results in a
+S.
100
Entropy, S
An exothermic reaction does not ensure spontaneity.
For example, the freezing of water is exothermic but
spontaneous only below 0
o
C.
An increase in disorder of the system also does not
insure spontaneity.
It is a proper combination of exothermicity and
disorder that determines spontaneity.
101
Entropy, S
If the entropy of a system increases during a
process, the spontaneity of the process is favored
but not required.
The Second Law of Thermodynamics says that the
entropy of the universe (not the system)
increases during a spontaneous process:
S
universe
= S
system
+ S
surroundings
> 0
102
Entropy, S
The entropy of a system can decrease during a
spontaneous process or increase during a
nonspontaneous process, depending on the
accompanying S
surroundings.
The actual system and its surroundings constitute
an isolated system.
We must consider any system as part of a larger
isolated system that includes the surroundings of
the system in which we are interested.
18
103
Entropy, S
The change of entropy in the universe is
determined by considering the total entropy
change,
S
tot
(universe)= S + S
surr
S = change of entropy in the system
S
surr
= change of entropy in the surroundings
If the total entropy change is positive, then the
process will be spontaneous.
104
Entropy, S
A process in which the S decreases (becomes more
organized) may be spontaneous if the change of
entropy in the S
surr
is so great that the S
tot
increases.
Example, the freezing of H
2
O.
105
Molar entropy of liquid H
2
O
Molar entropy of solid H
2
O
65.2 J/K mol
43.2 J/ K mol
22.0 J/K mol
When water freezes at O
o
C, its entropy decreases by 22.0 J/K
mol. However it is a spontaneous reaction.
106
Entropy, S
To explain the spontaneous process of freezing
water, we will determine if the change in
entropy is greater for the surroundings:
We can use the following relationship assuming
constant temperature and pressure of the
surroundings.
If the change of enthalpy of the system is H,
then, for transfer of heat at constant pressure, q
surr
= H
T
H
S
surr

=
107
Entropy, S
We can expect the entropy of the surroundings to
increase because freezing is an exothermic
process.
Adding heat to the surroundings creates more
disorder by stirring up the thermal motion of atoms
in the surroundings.
To determine how much the heat given off by the
freezing of water increases the entropy of the
surroundings, we can use any temperature just
below 0
o
C.
108
K mol
J
K
mol J
S
Table from
mol
kJ
H
K C T
T
H
S
surr
fus
o
surr
4 . 22
268
/ 10 01 . 6
) 3 . 6 (
01 . 6
268 273 0 . 5
3
=

=
=
= + =
=
Lets calculate the S
surr
at a temperature of -5.0
o
C.
The S
surr
is greater than the decrease in entropy of the system.
As more heat is released, and the temperature of the system
becomes lower, the entropy of the surroundings increases even
more.
> 22.0 J/mol K
19
109
Entropy, S
What we have learned is that the process may be
spontaneous, even if the system is becoming more
ordered (S)
if the heat energy released into the surroundings is
great enough to produce a positive overall change
of entropy in the isolated system(under
conditions of constant temperature and pressure of
the surroundings).
110
Entropy, S
Therefore, to use the entropy to judge the direction
of spontaneous change:
the change in entropy of the system plus the change
in entropy in the surroundings must be considered.
111
Entropy, S
If the total change in entropy is positive, the process
is spontaneous.
If the total change in entropy is negative, then the
reverse process is spontaneous.
The criterion for spontaneity is an increase in the
total entropy, not a decrease in the energy of the
system.
112
Entropy, S
In an exothermic
reaction:
a). Where the
entropy of the
system has
increased and the
entropy of the
surroundings has
increased.
The total entropy
of the isolated
system is positive.
In an exothermic
reaction:
b). Where the entropy
of the system has
decreased and the
entropy of the
surroundings has
increased.
The total entropy of
the isolated system is
positive.
113
In an endothermic reaction:
the entropy of the system
increases while the entropy of
the surroundings decreases.
There can be an overall
increase in entropy if the
disorder of the system increases
enough.
114
Entropy, S
Example: Is the formation of benzene spontaneous when it is
formed from its elements in their most stable state forms?
6 C (s) + 3 H
2
(g) C
6
H
6
(l)
Given:
H
o
= +49.0 kJ S
tot
= S
o
+ S
surr
S
o
= 253.18 J/K
T = 298K at standard state
K
J
K
J
T
H
S
surr
43 . 164
298
49000
=
+
=
=
S
tot
= (253.18 J/K) + (164.43 J/K)
= 417.61 J/K
NO, it is not spontaneous
20
115
Entropy, S
The only conditions in which a process cannot be
spontaneous are:
+ H and S
Under these conditions the process is absorbing heat
and becoming more ordered.
Under these conditions the process is decreasing the
entropy of the surroundings and decreasing the entropy
of the system.
Under these conditions, the total entropy change is
negative.
116
Entropy, S
Entropy changes for reactions can be determined
similarly to H for reactions.
o
reactants
n
o
products
n
o
298
S n S n S

=
117
Entropy, S
Example: Calculate the entropy change for the
following reaction at 25
o
C. Use appendix 2A.
2(g) 2 4(g)
2 NO N O
118
Entropy, S
2 4(g) 2(g)
2(g) 2 4(g)
o o o
rxn products reactants
n n
o o
N O NO
J J
mol K mol K
J kJ
mol K mol K
2 NO N O
S n S n S
S 2S
(304.2 ) 2(240.0 )
175.8 or -0.1758
=
=
=
=

The negative sign of S indicates that the system is more
ordered.
If the reaction is reversed the sign of S changes.
For the reverse reaction S
o
298
= +0.1758 kJ/ mol K
The + sign indicates the system is more
disordered.
119
Entropy, S
Example 2: Calculate S
o
298
for the reaction
below. Use appendix k.
( ) ( ) ( )
+
g 2 g 2 g
NO O N NO 3
120
Entropy, S
( ) ( ) ( )
( ) ( ) ( )
( )
2 g 2 g g
2 g g 2 g
0 0 0 0
298 N O NO NO
J
mol K
J kJ
mol K mol K
3 NO N O NO
S S S 3 S
219.7 240.0 - 3 210.4
172.4 or -0.1724
+
= +
= + (

=
Changes in S are usually quite small compared to E and
H.
Notice that S has units of only a fraction of a kJ
while E and H values are much larger numbers of
kJ.
21
121
Determining S: Examples
Determine if the change of entropy is negative or positive
without calculating the change in entropy
1. H
2
O (s) H
2
O (l)
2. H
2
O (g) H
2
O (l)
3. PCl
3
(g) + Cl
2
(g) PCl
5
(g)
4. 2 N
2
O
5
(g) 4 NO
2
(g) + O
2
(g)
5. MgSO
4
7H
2
O (s) MgSO
4
(s) + 7 H
2
O (g)
6. HCl (g) + H
2
O (l) H
3
O
+
(aq) + Cl
-
(aq)
+S
-S
+S
-S
+S
-S
122
Equilibrium
The tendency of reactions to proceed toward
equilibrium is the basis of much of chemistry.
A system at equilibrium does not change in either the
forward or reverse direction.
A system at equilibrium remains in its current state
until it is disturbed by changing conditions.
123
Equilibrium
For a system in dynamic equilibrium, the forward
and reverse processes continue but have equal rates.
E.g. a block of metal is at the same temperature as its
surroundings. (thermal equilibrium)
There is no net change in the flow of heat energy
into or out of the block of metal or the
surroundings.
E.g. a gas compressed by a piston in a cylinder.
(mechanical equilibrium)
The pressure of the gas is the same as its
surroundings and the gas does not expand or
contrast.
124
Equilibrium
A solid in contact with its liquid form is in dynamic
equilibrium.
2 2
0 1.0
forward
o
H O H O
reverse
ice liquid Cat atm
A liquid in contact with its gas form is in dynamic

equilibrium.
2 2
100 1.0
forward
o
H O H O
reverse
liquid gas Cat atm
125
Equilibrium
Chemical equilibrium occurs when a reaction mixture
reaches a certain composition:
forward
reverse
reactants products
The rate of reactants forming products equals the rate in which

products are degraded back to reactants.
126
Equilibrium
The common characteristic of any system in dynamic
equilibrium is that the processes have no net tendency
for the system to change either in the forward or
reverse direction.
Neither the forward process nor the reverse process is
spontaneous.
At equilibrium: S
tot
= 0
22
127
Free Energy Change, G, and Spontaneity
In the mid 1800s J. Willard Gibbs determined the
relationship of enthalpy, H, and entropy, S, that best describes
the maximum useful energy obtainable in the form of work
from a process at constant temperature and pressure.
The relationship also describes the spontaneity of a system.
The relationship is a new state function, G, the Gibbs Free
Energy.
128
The free energy change is a measure of the change in
the total entropy of a system and its surroundings at
constant temperature and pressure.
Spontaneous processes at constant temperature and
pressure are accompanied by a decrease in free
energy.
129
The total entropy change, S
tot
, is the sum of the
changes in the system, S, and its surroundings,
S
surr
:
S
tot
= S + S
surr
For a process at constant pressure and temperature,
the change in entropy of the surroundings:
tot
S
H
S at constant T and P
T
=
130
G = H- T S (at constant T & P)
Gibbs free energy relationship is defined solely in terms of state
functions, and therefore; G is a state function.
A negative G means there is a decrease in free energy.
At constant temperature and pressure, the direction of
spontaneous change is the direction of decreasing free
energy.
131
The change in the Gibbs Free Energy, G, is a
reliable indicator of spontaneity of a physical
process or chemical reaction.
G does not tell us how quickly the process occurs.
Chemical kinetics, the subject of Chapter 15, indicates the
rate of a reaction.
Sign conventions for G.
G > 0 reaction is nonspontaneous
G = 0 system is at equilibrium
G < 0 reaction is spontaneous
132
23
133
Free Energy Change, G,
and Spontaneity
As the temperature is increased, the free energy of a
substance decreases at constant pressure.
G = H TS
The entropy of a pure substance is almost always
positive, therefore; as the temperature increases the TS
increases as well.
The decrease in free energy with temperature is greater
for gases than liquids
The decrease in free energy with temperature is greater
for liquids than solids
134
Standard Reaction Gibbs Free Energy
The thermodynamic method used to determine spontaneity
for a chemical reaction is the standard reaction Gibbs
energy, G
r
, also known as standard reaction free
energy.
The difference in molar free energies, G
m
, of the
products and reactants.
The standard reaction free energy is the difference
between the pure products and pure reactants in
their standard states.
( ) ( ) ts tan reac G n products G n G
o
m
n
o
m
n
0
r
=

135
Because the absolute free energies of substances are not
known, the standard free energies of formation of
substances can be calculated.
The standard Gibbs free energy of formation, G
f
o
, of
a substance is the standard reaction free energy per
mole for the formation of a compound from its
elements in their most stable form.
The state with the lowest free energy is the most
stable form of an element
136
The standard free
energies of
formation of
elements in their
most stable forms is
zero.
G
f
o
(O
2,
g) = 0
137
The standard free energy of formation at a given
temperature indicates the stability of a compound when
compared to its elements under standard conditions (1.0
atm).
If
The pure compound has a lower free energy than that
of its pure elements.
The elements will likely change spontaneously into the
compound at that given temperature.
The compound is more stable than the elements under
standard conditions.
e temperatur given a at , 0 G
0
f
<
138
If
The free energy of the compound is higher than the
free energy of its elements.
The compound will more likely change spontaneously
into its pure elements.
The pure elements are more stable than the pure
compound.
e temperatur given a at , 0 G
0
f
>
24
139
A thermodynamically stable compound has a
G
f
.
A thermodynamically unstable has a +G
f
.
Although a compound may be predisposed to
spontaneously decompose into its elements, the actual
decomposition may take a very long time.
E.g. The G
f
for benzene, C
6
H
6
, is positive, however, it
has an indefinite self-life.
140
Substances that have a positive free energy of
formation but survive for long periods are called
nonlabile or even inert.
Substances that have a positive free energy of
formation and decompose rapidly are called labile.
141
Stable and unstable are terms that refer to the
thermodynamic tendency of a substance to
decompose into its elements.
Labile, nonlabile and inert are terms that refer to the
rate at which an unstable substance will decompose.
142
Changes in free energy obey the same type of
relationship we have described for enthalpy, H, and
entropy, S, changes.
0
reactants
n
0
products
n
0
298
G n G n G =

143
144
Example: Calculate G
o
298
for the reaction below.
Use appendix 2A.
3 8( ) 2(g) 2(g) 2 ( )
C H 5 O 3 CO 4 H O + +

25
145
G
o
298
< 0, so the reaction is spontaneous at standard
state conditions.
If the reaction is reversed:
G
o
298
> 0, and the reaction is nonspontaneous at
standard state conditions.
2(g) 2 ( ) 3 8 2(g) (g)
3 8(g) 2(g) 2(g) 2 ( )
o o o o o
rxn f CO f H O f C H f O
kJ
mol
kJ
mol
C H 5 O 3 CO 4 H O
G [3 G 4 G ] [ G 5 G ]
{[3( 394.4) 4( 237.3) [( 23.49) 5(0)]}
2108.5
+ +
= + +
= + +
=
146
The Temperature Dependence of Spontaneity
Free energy has the relationship G = H -TS.
Because 0 H 0 and 0 S 0, there are four
possibilities for G.
H S G Forward reaction spontaneity
+ Spontaneous at all Ts.
T dependent Spontaneous at low Ts.
+ + T dependent Spontaneous at high Ts.
+ + Nonspontaneous at all Ts.
147
Example: Calculate S
o
298
for the following reaction. Given that
H
o
298
= -2219.9 kJ, and G
o
298
= -2108.5 kJ.
5 12( ) 2(g) 2(g) 2 ( )
o o o
o o o
o o
o
C H 8 O 5 CO 6 H O
G H T S
H G T S
H G
S
T
+ +
=
=

=

148
( )
o
o
2219.9 2108.5 kJ
S
298 K
kJ J
S 0.374 374
K K
(

=
= =
149
S
o
298
= -374 J/K which indicates that the disorder
of the system decreases .
For the reverse reaction,
5 CO
2(g)
+ 6 H
2
O
(l)
C
5
H
12(l)
+ 8 O
2(g)
S
o
298
= +374 J/K which indicates that the
disorder of the system increases .
150
Example: Use thermodynamic data to estimate the
normal boiling point of water.
2 ( ) 2 (g)
H O H O
Because this is an equlibrium process G 0.
H
Thus H T S and T
S
= =
26
151
| |
assume H@ BP H
H H H
H
H kJ@25 C
298
o
o
H O
o
H O
o
o
J
K
o o
2 (g) 2 ( )

=
=
= +
l
241 8 285 8
44 0
. ( . )
.
152
( ) ( )
| |
K
kJ
K
J
0
rxn
K
J
0
rxn
0
O H
0
O H
0
rxn
0
rxn
0.1188 or 8 . 118 S
91 . 69 7 . 188 S
S S S
S BP @ S assume
2 g 2
=
=
=

153
T =
H
S
H
S
.0 kJ
0.1188
K
370 K - 273 K = 97 C
o
o
kJ
K
o
= =
44
370
154
Example: What is the percent error in the example?
( )
% error =
370- 373 K
K
error
% error of less than 1%!!
373
100% 080% = .
155
End of Chapter 15b
Fireworks are beautiful exothermic
chemical reactions.

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1

is done on system by surroundings.

A liquid in contact with its gas form is in dynamic

The rate of reactants forming products equals the rate in which

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