Thermodynamics-First Law

Work and Energy
Chapter 15b
Work motion against an opposing force.
Thermodynamics: The First Law
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 kgm2s2
Work and Energy
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:
The absolute value of internal energy of a system cannot

be measured.
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.
Instead, the change in internal energy is measured.

X means a change in (a difference in) the property of X.
X = Xfinal Xinitial
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.
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
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.
Winding a spring increases the potential energy
The hot compressed gas can do more work than a cooler

gas that is not compressed.
Highest point of potential

(stored) energy. E is positive
Passing an electric current through a system, such as

charging a battery, increases the batterys capacity to
do work.
Lowest point of potential

(stored) energy. E is
negative
5
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.
Work and Energy
Increasing internal energy would have a positive value.
If work is done by the system, the internal energy of

the system decreases.
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
Decreasing internal energy would have a negative

value.
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.
Work = force distance
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 = PexV
w = Pex (V2 V1)
This equation is applicable only to systems in which the
external pressure is constant during expansion.
distance = h (the distance the piston moves)

Work = force h
F
rearranging F = P A
A
F = force
P=
A = area
Substituting F in the work equation with P A :
Work = P A h
Volume of a cylinder = A h
V = A h
Figure 9.4: The piston moving a

distance
Work = P V
10
Work and Energy
The work expression describes the magnitude of work to

expand a gas by the change in volume against a pressure.
The piston is held

in place by an
external pressure.
w = PV
When a gas expands against a pressure, then the system is

doing work on the surroundings.
The external
pressure ,
atmospheric
pressure, is the
force opposing
expansion.
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:
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.
w = P V
11
12
Work and Energy
Work and Energy
If the external pressure is expressed in SI units of

Pascal's and change in volume is expressed in m3.
1 Pa = 1 kg m 1 s 2
(1 Pa ) ( m3 )
1 kg 3
1 kg m
m ) =
2 (
s2
m s
If the pressure is expressed in atmospheres and

the volume is in liters:
103 cm3 1 m 3 101.325 103 Pa

6 3
= 101.325 Pa m 3
1 L atm
1 atm
L 10 cm
= 1 joule
101.325 Pa m 3 = 101.325 joule
13
14
Work and Energy
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.
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.
15
Heat
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:
16
In an system that is not insulated:
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.
17
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.
18
Heat
Heat
q > 0 if heat is absorbed by the system.
Energy that is transferred as heat (q) is measured in

joules.
cal = 4.184 J
Cal = 1kcal = 4.184 x 103 J
(Cal is the nutritional calorie)
The sign of q represents whether heat has entered or
left 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
19
20
Heat
Surroundings
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
21
Figure 9.2: Combustion of methane

releases the quantity of energy
22
Figure 9.3: Energy diagram for the

reaction of nitrogen and oxygen
Exothermic process
Endothermic process
+ E; the internal energy of

the system has increased
E; the internal energy of

the system has decreased
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) + heat
N2 (g) + O2 (g) + heat

23
2NO (g)
24
NH4SCN plus
Ba(OH)2 8H2O is an
endothermic reaction
that causes
atmospheric H2O
vapor to freeze on the
outside of the beaker.
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.
25
26
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
27
Changes in Internal Energy
Example: If 1200 joules of heat are added to a

system in energy state E1, and the system does
800 joules of work on the surroundings, what is
the :
1. The energy change for the system, Esys?
2. The energy change of the surroundings,

Esurr?
E surr = 400 J
3. The energy of the system in the new state, E2?
E sys = E 2 - E1
E = E 2 - E1 = q + w
E = 1200 J + (-800 J)
E 2 = E1 + E sys
E = 400 J
= E1 + 400 J
E sys = + 400 J
29
30
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.
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.
Some powdered dry ice
(solid CO2) is placed into a
flexible bag, which is then
sealed.
If E = q, then E = + 1300 J
31
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
As the dry ice absorbs heat from the

surroundings, some solid CO2
sublimes to form gaseous CO2. The
larger volume of gas causes the bag to
expand. The expanding gas does the
work of raising a book that has been
32
placed on the bag.
or w = P (V2 V1)
force
F
Pressure is force per P =
= 2
area
d
unit area.
Volume is distance V = d 3
cubed.
PV is a work term, i.e., the same units are used for
energy and work.
F
P V = 2 d 3 = F d w hich is w ork
d
( )
33
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.
In constant-volume reactions, no PV is done.
34
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
A gas is produced but the

system cannot do work by
expanding the walls are too
rigid, the volume is constant.
CO2 ( s)
heat
CO2 ( g )
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
35
36
the gas does work as it expands against the pressure of the

atmosphere.
2 H2 (g) + O2 (g) 2 H2O (g)
If no heat is absorbed during the expansion:
For example: the complete reaction of a 2:1 mole ratio

of H2 and O2 gases to produce steam at some constant
temperature above 100oC and at 1.0 atm.
When a gas is produced against constant external

pressure, such as in an open vessel at atmospheric
pressure:
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.

37
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.
38
2 H2 (g) + O2 (g) 2 H2O (g)
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.
3 mol gases
2 mol gases
The internal energy of the

system increases by an
amount equal to the amount
of work done on it.
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,
ngas.
PV = nR T
P ( V ) = n g as R T
ngas = (number of moles of gaseous products)

(number of moles of gaseous reactants)
39
Fig. 15-7, p.606
40
When
Work is defined as a force acting through a specified

distance.
w = F d
= P V
1. V2 = V1
= ( n gas ) RT
Thus we can see that w = ( n gas ) RT
2. V2 > V1
at constant T and P.
Consequently, there are three possibilities for volume

changes:
3. V2 < V1
41
Then
Examples
V1
V2
PV = 0
ngas = 0
CO (g) + H 2 O (g) H 2 (g) + CO 2(g)

PV > 0
ngas > 0
Zn (s) + 2 HCl(aq) ZnCl2(aq) + H 2(g)

PV < 0
ngas < 0
N
+ 3 H 2(g) 2 NH 3(g)
2(g)

2 mol gas
0 mol gas
4 mol gas
2 mol gas
1 mol gas
2 mol gas
42
Consider the following gas phase reaction at

constant pressure at 200oC.
Consider the following gas phase reaction at constant

pressure at 1000oC.
PCl 5(g ) PCl 3(g ) + Cl 2(g )

2 NO( g ) + O 2( g ) 2 NO 2( g )

3 mol gas
1 mol gas
2 mol gas
V2 > V1 thus V > 0 and PV > 0.
2 mol gas
V2 < V1 thus V < 0 and PV < 0.

The reaction produces less moles of gas than in the original reactants.
The constant pressure exerted by the atmosphere decreased the volume.
Consequently, w = PV > 0.
Work is done on system by surroundings.
The increase in volume was a result of more moles of gas products than reactants.
The increase of gas products increases volume against constant pressure.
Consequently, w = PV < 0.
Work is done by the system on the surroundings. The internal energy of the system
decreases by the amount of work done by the system.
43
Relationship of H and E
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.
44
The enthalpy change is equal to the enthalpy or heat content of

the substances produced minus the enthalpy of the substances
consumed.
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
H = Hfinal Hinitial
H = Hsubstances produced Hsubstances consumed
45
46
We defined enthalpy as H = qP. (qp = 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 = qP.
For reactions in which the volume change is very

small or equal to zero.
For small volume changes,

V 0 and PV 0.
Since H = E + PV then
H E.
For no volume change,
H = E.
47
48
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.
E is positive when energy is absorbed by a system

undergoing a chemical or physical change at constant
pressure and constant volume.
C5 H12 (A ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O (A ) + 3.516 103 kJ
Energy can be written as a reactant of the process.
5 CO2(g) + 6 H2O(A) + 3.516 103 kJ C5H12(A) + 8 O2(g)
Indicates the
release of energy
Indicates the
absorption of energy
H = 3.516 103 kJ
H = + 3.516 10 kJ
-or-
-or-
E = 3.516 103 kJ
E = + 3.516 103 kJ
49
When heat energy has been transferred to a constantpressure system, the enthalpy of the system increases by
that amount.
When heat energy has been released from constantpressure system, the enthalpy of the system decreases by
that amount.
50
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.
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.
Zn (s) + I2 (s) ZnI2 (s)

51
52
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
Example: Given that the combustion of n-pentane, nC5H12, 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?
C 5 H12( A ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O ( A )
When the reaction absorbs

208 kJ of heat at constant
pressure, the reservoir rises
by 208 kJ and the H =
+208kJ
8 mol of gas
53
5 mol of gas
54
Determine the work done by this reaction.
E = q + w
H = 3523 kJ
w = + 7.422 kJ
C5 H12(A ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O (A )

8 mol gas
Now calculate the E for this reaction from the values

of H and w that we have determined.
5 mol gas
H = -3523 kJ/mol, T = 298 K.

w = -PV = -(n gas )RT
E = ( 3523 kJ ) + ( +7.422 kJ )
n gas = 5 8 mol = -3 mol
= 3516 kJ
w = -(-3 mol)(8.314 J mol K )(298 K) = 7433 J = 7.433 kJ

work is done on the system by the surroundings
Remember, work is done on the system by the surroundings;

therefore, work is positive.
55
56
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)
The reaction of 1.00 mole of H2(g) with 0.500 mole

of O2(g) to produce 1.00 mole of steam, H2O(g), at
100C and 1.00 atm pressure evolves 242 kJ of heat.
Calculate E per mole of H2O(g) produced. The
universal gas constant is 8.314 J/molK.
We will calculate this problem in class.
We will calculate this one in class.
57
Spontaneous Changes
A spontaneous change has a natural direction.
For example the rusting of iron occurs spontaneously.
Spontaneous Changes
Spontaneous changes happen without any continuing

outside influences.
58
Have you ever seen rust turn into iron metal without
man made interference?
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.
The melting of ice at room temperature occurs

spontaneously.
Will water spontaneously freeze at room temperature?
59
60
10
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 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 randomly moving molecules of a gas spread

throughout their containers
The change in the entropy of the universe for a given

process is a measure of the driving force behind that
process.
It is highly improvable that the random motion of gases

will bring them all simultaneously back into one corner of
the container.
61
Energy and matter tend to become more disordered.

In thermodynamics, this idea of a tendency toward
disorder is call entropy (S).
62
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.
High disorder represents high entropy.

Low disorder represents low entropy.
Nature tends to spontaneously proceed to a state which

has the highest probability of existence.
63
Figure 10.3: Expansion of an ideal gas into an evacuated

bulb
64
Figure 10.4: Three possible arrangements

(states) of four molecules.
Gases are
distributed
evenly when
allowed to
expand into an
evacuated bulb.
65
66
11
If there are two

molecules in the twobulbed flask, there is one
chance in four that both
molecules will be in the
left bulb.
Arrangement I only one

possible arrangement, all
the molecules must be at
one end of the twobulbed 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.
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.
67
68
Changes in Entropy
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
The entropy of an isolated system increases during

the course of a spontaneous change.
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.
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.
69
Changes in Entropy
Changes in Entropy
Example:
a) Calculate the change in entropy in 1.0 L of water at
0.oC when it absorbs 235 J of energy from a heater.
b) If the 1.0 L of water is at 99oC, what is the change in
entropy?
c) Explain any difference in entropy change.
Provided that the temperature is constant, the change in

the entropy of a system can be calculated from the
following expression:
S =
qrev
T
Where qrev signifies that the energy must be transferred

reversibily (through an infinite number of steps).
70
For a reversible transfer of energy as heat, the

temperatures of the surroundings and the system
must be only infinitesimally different.
71
72
12
Changes in Entropy
a ) 0.0 o C = 0. 0 + 273 = 273 K

H = 235 J
q
H 235 J 0.861 J
S = rev =
=
=
T
T
273 K
K
Heat added to system is

endothermic.
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.
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.
b) 99o C = 99 + 273 = 372 K

q
H 235 J 0.632J
S = rev =
=
=
T
T
372 K
K
c) The change in entropy is smaller for the water at higher

temperatures because the water molecules are already more
chaotic.
Heating increases the thermal disorder.
Spreading the molecules of a substance into additional

locations increases the positional disorder.
At lower temperatures, the same amount of heat transferred to

the water had a greater effect on changes in entropy.
73
Changes in Entropy
74
Changes in Entropy
Example: A sample of 0.0410 mol of N2 gas is

heated from 20.0 oC to 400.oC 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.
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.
75
Entropy, S
Entropy, S, of Changing Physical States
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 So298
When:
76
During physical changes:
S > 0 disorder increases (which favors spontaneity).

S < 0 disorder decreases (does not favor
spontaneity).
77
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.
78
13
Entropy, S
From the Second Law of Thermodynamics, for a spontaneous

process to occur:
Suniverse = Ssystem + Ssurroundings > 0
In general for a substance in its three states of matter:
Sgas > Sliquid > Ssolid
79
1.

2. At the temperature of a phase transition, the
transfer of heat is reversible.
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:
At the transition temperature, the temperature of
the substance remains constant as heat is
supplied.
80
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.
E.g., the temperature remains at 100.0 oC (at 1.0

atm) when water is vaporized from a liquid to a
gas.
81
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, Hvap.
(qrev = Hvap)
The entropy of vaporization at the normal
boiling point is
H
S =
82
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:
o
Svap
vap
All standard entropies of vaporization are

positive (becoming more disorganized) and are,
therefore; reported without their positive signs.
Tb
83
84
14
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:.
S fus =
H ofus
Tf
85

Example: Calculate the entropy change for:
a) The vaporization of 1.00 mol of H2O(l) at 100. oC.
b) The freezing of 3.33 g of C2H5OH at 158.7K. The
Hfus = 4.60 kJ/mol K
The freezing of 3.33 g of C2H5OH at 158.7K. Hfus = 4.60 kJ/mol K

b)
4600 J
mol
H fus
4600 J/mol
q
28.99 J
S =
=
=
=
158.7 K
T
T
K mol
(1.0 mol C 2 H 5OH ) 28.99 J

J
( 3.33 g C2 H5OH )

= 2.09
K
46.07 g C 2 H 5OH K mol
H fus
kJ
; T = 100. + 273 = 373 K
mol
J
The units of S are
K mol
H vap = 40.7
a)
S =
86
for C2 H 5OH =
C2 H 5OH
109 J
q H 40700 J / mol
=
=
=
373K
T
T
K mol
87
Molecular Interpretation of Entropy
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.
88
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.
89
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
90
15
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.
E.g. A sample of CO molecules at a temperature

close to T=0 has a residual entropy of 4.6 JK1.
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.
91
92
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 24
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.
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.
93
Standard Molar Entropies
94
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.
95
96
16
Standard Reaction Entropies
Entropy is useful as a predictor of the natural

direction of a reaction.
Often, we can predict the sign of the entropy

change of a system without calculations.
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.
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.
97
Entropy, S
98
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.
An exothermic reaction does not ensure spontaneity.
For example, the freezing of water is exothermic but

spontaneous only below 0oC.
An increase in disorder of the system also does not

insure spontaneity.
It is a proper combination of exothermicity and
disorder that determines spontaneity.
99
Entropy, S
100
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
The entropy of a system can decrease during a

spontaneous process or increase during a
nonspontaneous process, depending on the
accompanying Ssurroundings.
The actual system and its surroundings constitute
an isolated system.
101
We must consider any system as part of a larger

isolated system that includes the surroundings of
the system in which we are interested.
102
17
Entropy, S
The change of entropy in the universe is

determined by considering the total entropy
change,
Stot (universe)= S + Ssurr
Entropy, S
S = change of entropy in the system

Ssurr = change of entropy in the surroundings
A process in which the S decreases (becomes more

organized) may be spontaneous if the change of
entropy in the Ssurr is so great that the Stot
increases.
Example, the freezing of H2O.
If the total entropy change is positive, then the

process will be spontaneous.
103
104
Entropy, S
Molar entropy of solid H2O

Molar entropy of liquid H2O
65.2 J/K mol
To explain the spontaneous process of freezing

water, we will determine if the change in
entropy is greater for the surroundings:
43.2 J/ K mol
22.0 J/K mol
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, qsurr
= H
H
S surr =
OoC,
When water freezes at

its entropy decreases by 22.0 J/K
mol. However it is a spontaneous reaction.
105
Lets calculate the Ssurr at a temperature of -5.0 oC.
Entropy, S
H
T
T = 5.0 oC + 273 = 268K
S surr =
We can expect the entropy of the surroundings to

increase because freezing is an exothermic
process.
106
H fus =
Adding heat to the surroundings creates more

disorder by stirring up the thermal motion of atoms
in the surroundings.
6.01 kJ
( from Table 6.3)
mol
S surr =
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 0oC.
6.01 103 J / mol

22.4 J
=
mol K
268 K
> 22.0 J/mol K
The Ssurr 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.
107
108
18
Entropy, S
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).
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.
109
Entropy, S
110
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.
In an exothermic
reaction:
In an exothermic
reaction:
a). Where the

entropy of the
system has
increased and the
entropy of the
surroundings has
increased.
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.
The total entropy

of the isolated
system is positive.
111
112
Entropy, S
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.
Example: Is the formation of benzene spontaneous when it is

formed from its elements in their most stable state forms?
6 C (s) + 3 H2 (g) C6H6 (l)
Given:
Ho = +49.0 kJ
Stot = So + Ssurr
So = 253.18 J/K
T = 298K at standard state
S surr =
H
+ 49000 J
J
=
= 164.43
298 K
T
K
Stot = (253.18 J/K) + (164.43 J/K)

= 417.61 J/K
NO, it is not spontaneous
113
114
19
Entropy, S
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.
Entropy changes for reactions can be determined

similarly to H for reactions.
So298 = nSoproducts nSoreactants

n
115
116
Entropy, S
Entropy, S
2 NO 2(g)
N 2 O 4(g)
S orxn =
Example: Calculate the entropy change for the

following reaction at 25oC. Use appendix 2A.
n S
o
products
n S oreactants
n
= S oN 2 O 4(g) 2S oNO 2(g)
N O
2 NO 2(g)
2 4(g)
= (304.2 J mol K ) 2(240.0 J mol K )

= 175.8 J mol K or -0.1758 kJ mol K
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 So298= +0.1758 kJ/ mol K
The + sign indicates the system is more

disordered.
117
118
Entropy, S
3 NO( g )
N 2 O( g ) + NO 2( g )
Entropy, S
S0298 =
Example 2: Calculate So298 for the reaction

below. Use appendix k.
S0N 2O(g) +
S0NO2(g ) 3 S0NO(g)
= 219.7 + 240.0 - 3 ( 210.4 ) J mol K
3 NO (g )
N 2 O (g ) + NO 2(g )
= 172.4 J mol K or -0.1724 kJ mol K
Changes in S are usually quite small compared to E and

H.
119
Notice that S has units of only a fraction of a kJ

while E and H values are much larger numbers of
kJ.
120
20
Determining S: Examples
Equilibrium
Determine if the change of entropy is negative or positive

without calculating the change in entropy
1.
2.
3.
4.
5.
6.
H2O (s) H2O (l) +S

H2O (g) H2O (l) -S
PCl3 (g) + Cl2 (g) PCl5 (g) -S
2 N2O5 (g) 4 NO2 (g) + O2 (g) +S
MgSO4 7H2O (s) MgSO4 (s) + 7 H2O (g) +S
HCl (g) + H2O (l) H3O+ (aq) + Cl- (aq) -S
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.
121
Equilibrium
122
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.
A solid in contact with its liquid form is in dynamic

equilibrium.
forward
liquid H O 0o C at 1.0 atm

iceH2O
2
reverse
A liquid in contact with its gas form is in dynamic

equilibrium.
forward
gasH O 100o C at 1.0 atm

liquid H2O
2
reverse
123
Equilibrium
124
Equilibrium
Chemical equilibrium occurs when a reaction mixture

reaches a certain composition:
forward
products
reactants
reverse
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.
The rate of reactants forming products equals the rate in which

products are degraded back to reactants.
125
Neither the forward process nor the reverse process is

spontaneous.
At equilibrium: Stot = 0
126
21
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.
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.
127
The total entropy change, Stot, is the sum of the

changes in the system, S, and its surroundings,
Ssurr:
Gibbs free energy relationship is defined solely in terms of state

functions, and therefore; G is a state function.
G = H - TS
Stot = S + Ssurr
(at constant T & P)
A negative G means there is a decrease in free energy.
For a process at constant pressure and temperature,

the change in entropy of the surroundings:
Stot = S
128
At constant temperature and pressure, the direction of

spontaneous change is the direction of decreasing free
energy.
H
at constant T and P
T
129
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.
130
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
131
132
22
Free Energy Change, G,

and Spontaneity
Standard Reaction Gibbs Free Energy
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
The thermodynamic method used to determine spontaneity

for a chemical reaction is the standard reaction Gibbs
energy, Gr, also known as standard reaction free
energy.
G0r = nGom (products) nGom (reactan ts)

n
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.
133
134
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, Gfo, 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
The standard free

energies of
formation of
elements in their
most stable forms is
zero.
Gfo (O2, g) = 0
135
136
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).
0
If G f < 0, at a given temperature
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.
If
137
G0f > 0, at a given temperature

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.
138
23
A thermodynamically stable compound has a

Gf.
A thermodynamically unstable has a +Gf.
Although a compound may be predisposed to

spontaneously decompose into its elements, the actual
decomposition may take a very long time.
E.g. The Gf for benzene, C6H6, is positive, however, it
has an indefinite self-life.
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.
139
140
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.
Changes in free energy obey the same type of

relationship we have described for enthalpy, H, and
entropy, S, changes.
G 0298 = nG 0products nG 0reactants

n
141
142
Example: Calculate Go298 for the reaction below.

Use appendix 2A.
C3H8(A ) + 5 O2(g) 3 CO2(g) + 4 H2O(A )
143
144
24
The Temperature Dependence of Spontaneity
C 3 H 8(g) + 5 O 2(g) 3 CO 2(g) + 4 H 2 O (A )
G orxn = [3 G fo CO 2(g) + 4 G fo H 2 O (A ) ] [ G fo C 3 H 8(g) + 5 G fo O 2(g) ]

= {[3( 394.4) + 4( 237.3) [( 23.49) + 5(0)]} kJ mol
= 2108.5 kJ mol
+
+
Go298 < 0, so the reaction is spontaneous at standard

state conditions.
If the reaction is reversed:
Free energy has the relationship G = H -TS.

Because 0 H 0 and 0 S 0, there are four
possibilities for G.
Go298 > 0, and the reaction is nonspontaneous at

standard state conditions.
T dependent
T dependent
Forward reaction spontaneity
Spontaneous at all Ts.

Spontaneous at low Ts.
Spontaneous at high Ts.
Nonspontaneous at all Ts.
145
146
Example: Calculate So298 for the following reaction. Given that

Ho298= -2219.9 kJ, and Go298= -2108.5 kJ.
2219.9 ( 2108.5 ) kJ
So =
298 K
So = 0.374 kJ
= 374 J
K
K
C5 H12(A ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O(A )

G o = H o TSo
H o G o = TSo
H o G o
= So
T
147
148
So298 = -374 J/K which indicates that the disorder

of the system decreases .
For the reverse reaction,
5 CO2(g) + 6 H2O(l) C5H12(l) + 8 O2(g)
Example: Use thermodynamic data to estimate the

normal boiling point of water.
H O
H2O(A )
2 (g)
Because this is an equlibrium process G = 0.
H
Thus H = TS and T =
S
So298 = +374 J/K which indicates that the

disorder of the system increases .
149
150
25
assum e H @ B P H o298
o
H = H
o
H 2 O (g)
assume S @ BP S0rxn
o
H 2O ( l )
S0rxn = S0H 2O( g ) S0H 2O( A )
H o = [ 241.8 ( 285.8 ) ] J K
o
S0rxn = [188.7 69.91] J K
H = + 44 .0 kJ@ 25 C
S0rxn = 118.8 J K or 0.1188 kJ K
151

T =
152
H
H o
44 .0 kJ
=
= 370 K
0.1188 kJ K
S
So
Example: What is the percent error in the example?
370 K - 273 K = 97 o C
% error =
153
(370 - 373) K 100% = 0.80% error

373 K
% error of less than 1%!!
154
End of Chapter 15b
Fireworks are beautiful exothermic

chemical reactions.
155
26

Thermodynamics-First Law

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Thermodynamics-First Law

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Work and Energy

Work motion against an opposing force.

Thermodynamics: The First Law

A weight raised against the pull of gravity.

The work required to move an object a certain distance

Work and Energy

Work and Energy

The capacity of a system to do work is called internal

Internal energy is its total store of energy

The absolute value of internal energy of a system cannot

Kinetic energy of the molecules

Instead, the change in internal energy is measured.

Work and Energy

When work is done on a system, the internal energy

Compressing a gas inside a thermally insulated

Winding a spring increases the potential energy

The hot compressed gas can do more work than a cooler

Highest point of potential

Passing an electric current through a system, such as

Lowest point of potential

Work and Energy

As indicated by the text, we always take the

Work and Energy

Increasing internal energy would have a positive value.

If work is done by the system, the internal energy of

The symbol w is used to denote the energy transferred to

Decreasing internal energy would have a negative

E.g., compressing a gas in an insulated container

If energy leaves the system as work, the internal energy

E.g., allowing the gas to expand again.

Work = force distance

E.g., a gas expanding in a cylinder fitted with a piston

The work done by an expanding gas can be described by

distance = h (the distance the piston moves)

Figure 9.4: The piston moving a

Work and Energy

The work expression describes the magnitude of work to

The piston is held

When a gas expands against a pressure, then the system is

The system is losing internal energy in the form of work.

The V is increasing and is positive.

Since work must be negative when the internal energy of the

Work and Energy

Work and Energy

If the external pressure is expressed in SI units of

If the pressure is expressed in atmospheres and

103 cm3 1 m 3 101.325 103 Pa

101.325 Pa m 3 = 101.325 joule

Work and Energy

Work and Energy

2. Nonexpansion work involves work that does not

A chemical reaction can do nonexpansion work by

Free expansion describes a system in which

A system does no expansion work when it expands into

The internal energy within a system can also be

In an system that is not insulated:

Heat is energy that is transferred as a result of a

If the system is cooler than its surroundings, then

Energy that is transferred as heat (q) is measured in

q < 0 if heat is released by the system.

Exothermic processes: heat is released into the

Almost all chemical reactions and all combustion

Endothermic processes: heat is absorbed from the