SK2112/SC2242 Physical Chemistry II Chapter 6

Prepared by: Moh Pak Yan, SST, UMS 1

CHAPTER 6
THE FIRST LAW OF
THERMODYNAMICS
Energy cannot be created or destroyed
but it can be transformed. The total
amount of energy is constant - Energy is
conserved during any process
Work w or W is performed on an object when the object
moves some distance s due to a force F exerted on it
w = F s = |F||s|cos
where is the angle between the vectors and work is
scalar quantity.
Work has a unit of joules (J), like energy because work is
a way of energy transform
Energy is defined as the ability to do work, so it make
sense that energy and work have the same unit
Therefore, in a close system as shown in Fig. 6.1, the
system is doing work on the surrounding - hence, the
system is losing energy in the form of work - this implies
that the final energy inside the system is lower then the initial
energy
Work, Heat, and Internal Energy
dw
dq
Figure 6.1: The work is done by the system
The infinitesimal amount of work dw that the system
does on the surroundings for an infinitesimal change
of volume dV while acting against a constant external
pressure p
ext
is defined as:
The negative sign indicates that the work done
contributes to a decrease of the amount of energy in the
system
However, if piston moves inward, then the
surroundings are doing work on the system, and the
amount of energy in the system is increased
Note: In discussing the science of thermodynamics,
we have to focus on the system - either the work is
positive or negative with respect to the system not
surrounding
dw = p
ext
dV
1
dw dw
P P
ext ext dV dV
dw dw + + p p
ext ext
dv dv = 0 = 0
If all (infinite) the infinitesimal changes that
contribute to an overall change, the total amount of
work done on or by the system can be calculated by
the integration of Eqn. 1:
In this case, the limits on the integral are the initial
volume, V
i
, and the final volume, V
f
, of the process
If the external pressure is not constant throughout the
process, say keep the pressure changing in order to fix
the volume, so no work will be done on or by the
system - but however, the total energy will remain the
same. That is, the change of internal energy U
2a
V p ) V V ( p dV p w
ext i f ext
f
i
ext
D - = - - = - =


id3194732 pdfMachine by Broadgun Software - a great PDF writer! - a great PDF creator! - http://www.pdfmachine.com http://www.broadgun.com
SK2112/SC2242 Physical Chemistry II Chapter 6
Prepared by: Moh Pak Yan, SST, UMS 2
In many cases, the volume change is also due to
change in height of the system as shown in Fig. 6.2.
2b
Figure 6.2: When a piston of
area A moves out through a
distance n, it sweeps out a
volume V =A n. The
external pressure p
ext
oppose
the expansion with a force of
p
ext
A.
) (
1 2
h h A p dh A p w
ext ext rev
- - = - =

h
Fig. 6.3 illustrates a condition that occasionally occurs
with gases: the expansion of a gas into a larger
volume which is initially a vacuum
In such a case, since the gas is expanding against a p
ext
of zero, by the definition of work in Eqn. 2 the work
done by the gas equals zero - this process is called free
expansion
On the other hand, the various gas laws can be used
to help us calculate the amount of pressure-volume
work in term of changes in system volume - this is
especially for the reversible changes in which the
external pressure (surroundings) will equal to the
internal pressure (system) and therefore:
int int ext ext rev
dV p dV p w

= - =
3
Figure 6.3: No work is performed for
the free expansion of gas
Eqn. 3 can be related to the ideal gas equation of state
as follows (see Fig. 6.4):
For an isothermal, reversible change of an ideal gas,
we can substitute the expression p
i
/p
f
for the volume
and becomes:
4
i
f
rev
V
V
ln nRT dV
V
1
nRT w - = - =

5
f
i
rev
p
p
nRT dV
p
nRT w ln
1
- = - =

Figure 6.4: The work of
reversible, isothermal
expansion of a perfect
gas.
Note that, for a given
change of volume and
fixed amount of gas,
higher the temperature
the greater is the work.
Heat, symbolized by the letter q or Q , is a measure of
thermal energy transfer that can be determined by the
change of temperature of an object - heat is a type of
energy change in the system; it can be transferred into
or outside the system solely due to the temperature
difference between system and its surroundings
Heat is considered positive when it is added into the
system or when it crosses the boundary from the
surroundings into the system
In fact, for the same temperature change of two
different systems (materials) requires different
amount of heat - the amount of heat required to
change the temperature of 1.0 g of a material by 1.0
o
C
is called specific heat, c
c = Q / mAT
6
SK2112/SC2242 Physical Chemistry II Chapter 6
Prepared by: Moh Pak Yan, SST, UMS 3
The amount of heat required to raise the temperature of
a given mass of substance by 1.0
o
C is called heat
capacity, C
Internal Energy, U is the total energy of a system; it
composed of energy like chemical, electronic, nuclear, and
kinetic energies
It is impossible for us to measure the absolute total
internal energy of any system because we cannot
completely measure all types of energy in any system
For an isolated system, no passage of matter and energy
occurs between the system and surroundings. Therefore
the total energy of the system does not change:
Change of internal energy, U = 0 (isolated system)
C = Q / T
7
Indeed, we are more interested on energy changes of
the system - investigations of energy changes in
systems found that changes of internal energy of a
system will produce either work or heat, or both work and
heat
Note that only work and heat (or both) will accompany a
change in internal energy and this reflect the changes in
the total energy of a system
On the other hand, if the system is insulated well
enough, heat will not be able to get into or leave the
system - this is called adiabatic system with q = 0
Therefore, for adiabatic process,
U = q + u
8
U = u
9
If no work is performed
during the process, then
Two conditions for w = 0:
i. Free expansion
ii. Isochoric process
Figure 6.6: When work is
done on a system, its
internal energy rises. The
internal energy also rises
when energy is transferred
into the system as heat.
U = q
9
Note: Internal energy, U, is
an extensive property of a
sample: 2 kg of iron has twice
internal energy of 1 kg of
iron in the same condition.
On the other hand, the molar
internal energy, U
m
, is an
intensive property.
Figure 6.6: Sign Convention
w and q are positive if energy
enters the system (as work
and heat, respectively), but
negative if energy leaves the
system
Although the internal energy represents the total energy
of a system, and the first law of thermodynamics is based
on the concept of internal energy, it is not always the best
variable to work with
Eqn. 9 shows that the change of the internal energy is
exactly equal to q - of the volume of the system remains
constant for a particular process
However, the experimental condition of constant volume
can be difficult to guarantee for many processes - many
experiments carried out in the atmosphere and pressure
is often an easier parameter to be fixed (which is constant
pressure)
Internal energy cannot explain the real state/condition of
a system because it is almost impossible to obtain a
constant internal energy
Enthalpy
Figure 6.7: When a system is
subjected to a constant
pressure and is free to
change its volume, some of
the energy supplied as heat
may escape back into the
surroundings as work, In
such a case, the change in
internal energy is smaller
than the energy supplied as
heat
SK2112/SC2242 Physical Chemistry II Chapter 6
Prepared by: Moh Pak Yan, SST, UMS 4
Enthalpy is symbolized as H and it fundamental
definition is: H U + pV ; where the pressure in the
above equation is the system pressure, p
int
Enthalpy is a state function, and like internal energy,
the absolute value of the enthalpy is unknowable, but
we can determine changes of enthalpy, dH = dU + d(pV)
Rewrite the above equation by using chain rule of
calculus we will get: dH = dU + V dp + p dV
In a constant pressure process, the V dp = 0, and
substitute dU = dq + dw :
dH = dq + dw + p dV
= dq - p dV + p dV = dq
Hence, in term of overall (integral) changes of a system:
H = q
10
The changes of internal energy and enthalpy are dealt
with the overall change of a complete process - we have not
considered infinitesimal changes in U and H in much detail
Both the internal energy and the enthalpy of a given
system are determined by the state variables of the
system - that is, p , V, T and n for a gas
Lels iniliaIIy assune an unchanging anounl of gas (lul
this is quite impossible for a system involving chemical
reaction) - Therefore, U and H are determined by p, V,
and T alone which are related to the ideal gas law
Hence, if we want to understand the infinitesimal change
in a state function, we need only understand how it
varies with respect to two of the three state variable of p, V,
and T - the third state variable can be calculated from the
other two
Changes In State Functions & Heat Capacity
For the changes of internal energy, U, we need to know
the dT and dV whilst for the changes of enthalpy, H, we
need to know the dT and dp - the total differential of a state
function is written as the sum of the derivative of the function
with respect to each of its variables
The total infinitesimal change in U, dU, can be written
in terms of those slopes as shown in Fig. 6.8
Recall another definition for dU: dU = dq + dw = dq p dV.
If we equate these two definition of dU:
Solving for the change in heat, dq :
dV p dq dV
V
U
dT
T
U
dU
T V
- =

=
dV p
V
U
dT
T
U
dq
T V

=
11
Figure 6.8: The internal
energy of a system varies
with volume and temper-
ature, perhaps as shown
here by the surface. The
variation of the internal
energy with temperature
at one particular constant
volume is illustrated by
the cure drawn parallel to
T. The slope of this curve
at any points is the partial
derivative (U/oT)
V
Figure 6.9: The internal
energy of a system increases
as the temperature is raised;
this graph shows its variation
as the system is heated at
constant volume. The slope
of the tangent to the curve at
any temperature is the heat
capacity at constant volume
at that temperature, the heat
capacity is greater at B than
at A.
If the gaseous undergoes a change in isochoric system,
then dV = 0, therefore:
Above equation can be written with respect to
temperature change, which equals the infinitesimal
change of the internal energy, U, with respect to the
infinitesimal change of temperature, T, at constant
volume - this also defined as the constant volume heat
capacity of the system, C
V
Eqn. 12 is therefore can be written as:
Integration of both sides of infinitesimal change:
V
V
C dT
T
U
dq

=
12
dT C dq V =
13

D = =
f
i
T
T
V V
U dT C q
14
SK2112/SC2242 Physical Chemistry II Chapter 6
Prepared by: Moh Pak Yan, SST, UMS 5
If the heat capacity is constant over the temperature
range (for a small temperature ranges not involving
changes in phase), it can be taken out of the integral to
yield:
For n moles of gas:
with is molar heat capacity
By using the same way of derivative of infinitesimal
internal energy change, the infinitesimal enthalpy change
can be written as:
T C T T C dT C U
V i f V
T
T
V
f
i
D = - = = D

) (
15
T C n U
V
D = D
16

V
C
dp
p
H
dT
T
H
dH
T
p

=
17
If change occur in constant pressure, then p = 0 and
therefore:
The constantpressure heat capacity C
p
can be written as:
Integration of all infinitesimal enthalpy changes:
It can also be defined as molar heat capacity:
18
19
dT
T
H
dH
p

=
21
dT
dH
T
U
C
p
p
=

dT C n H
p
= D

= D = = D
f
i
T
T
p p p
q T C dT C H
20
Figure 6.3: No work is performed for
the free expansion of gas
Phase change (the change of state of matter and its
physical state) are determined by the interplay between
kinetic energy and intermolecular forces
Phase Change
Figure 6.10: Phase change of a matter
Figure 6.11: Heating curve of water
SK2112/SC2242 Physical Chemistry II Chapter 6
Prepared by: Moh Pak Yan, SST, UMS 6
In most cases, changes in phase occur under
experimental conditions of constant pressure, so that the
heat involved, q , is equal to H
Example: H
2
O (s, 0
o
C) H
2
O (l, 0
o
C)
a certain amount of heat is required per gram or per mole
in order to change the phase - however, during phase
change, the temperature does not change
Therefore Eqn. 6 does not apply because T = 0
Instead, the amount of heat involved is proportional to
the amount of material - the proportionality constant is
called the heat of fusion, H
fus
H
fus
= Q / m (unit: J/kg)
or
H
fus
= Q / n (unit: J/mol)
22
Changes in volume from solid to liquid, or from liquid to
solid are usually negligible, so H U (water is an
exception, it expands approximately 10% when freezing)
On the other hand, the change in of volume from a liquid
to a gas (or a solid to a gas) is considerable:
Example: H
2
O (l, 100
o
C) H
2
O (g, 100
o
C)
The proportionality constant for the vaporization process
is called the heat of vaporization, H
vap
It is common to neglect the volume of the condensed
phase, which is usually negligible
H
vap
= Q / m (unit: J/kg)
or
H
vap
= Q / n (unit: J/mol)
23
A chemical reaction will change the identities of the
system, which is called chemical change
There is a need to expand the applicability of U and H
Chemical change will change the U and H, which is
equal to the total enthalpy of the final condition (the
products) minus the total enthalpy of the initial
conditions (the reactants):
H
rxn
= H
f
H
i
= H
products
H
reactants
H
rxn
is the change of enthalpy for chemical reaction and
it is related to U
rxn
, the change of internal energy for
the chemic reaction
In Fig. 6.12, (a) shows the enthalpy change of a system
due to an endothermic reaction while (b) is due to an
exothermic reaction
Chemical Change
(a) (a)
(b) (b)
Figure 6.12:
(a) The amount of enthalpy is
going up, this means that
energy is going into the
system - endothermic
(b) The amount of energy is
going down, the system is
giving off energy into the
surroundings - exothermic
The change in energy of a chemical process depends on
the conditions of the process - pressure and temperature
The standard condition of pressure is 1 bar, which is
almost equal to 1 atm (1 bar = 1 x 10
5
Pa = 0.9869 atm)
There is no defined standard temperature, although many
thermodynamic measurements are reported for 298.15 K
Therefore, H
o
rxn
and U
o
rxn
, lhe '
o
indicales lhal lhe
change of enthalpy and the change of internal energy,
respectively, for the chemical reaction is measured in the
standard condition (temperatures are usually specified as
well. If not, take T = 25
o
C)
In the real situation, only relative values, change in
enthalpy, can be measured - we need a set of chemical
reactions whose H
rxn
values can serve as standards
against which all other H
rxn
values can be measured -
the Hesss Lav
Germain Henri Hess (1802 - 1850), a study-founder of
thermochemistry, studied the energy changes of chemical
reactions and realized that the following key ideas are
important in studying the energy changes that accompany
chemical reactions:
Specific chemical changes are accompanied by a
characteristic change in energy
New chemical changes can be devised by combining
known chemical changes - this can be done algebraically
The change in energy of the combined chemical reaction
is the equivalent algebraic combination of the energy
changes of the component chemical reaction
The alove ideas aie coIIecliveIy knovn as Hesss Lav and
are the fundamental basis of thermodynamics as applied
to chemical reaction
SK2112/SC2242 Physical Chemistry II Chapter 6
Prepared by: Moh Pak Yan, SST, UMS 7
A formation reaction is any reaction making 1 mole of a
products in the standard state
Enthalpy change of a formation reaction is called the
enthalpy of formation and designated H
o
f
Fe
2
O
3
(s) + 3SO
3
(l) Ie
2
(SO
4
)
3
(s) H
o
f
= certain value, kJ
Fe
2
(s) + 3/2 O
2
(g) Ie
2
O
3
(s) H
o
rxn
= 825.50 kJ
S (s) + 3/2 O
2
(g) SO
3
(l) H
o
rxn
= 438.00 kJ
2Fe (s) + 3S (s) + 6O
2
(g) Ie
2
(SO
4
)
3
(s) H
o
rxn
= 2583.0 kJ
Fe
2
O
3
(s) Ie
2
(s) + 3/2 O
2
(g) H
o
rxn
= + 825.50 kJ
3[SO
3
(g) S (s) + 3/2 O
2
(g)] H
o
rxn
= + 1314.00 kJ
2Fe (s) + 3S (s) + 6O
2
(g) Ie
2
(SO
4
)
3
(s) H
o
rxn
= 2583.00kJ
Fe
2
O
3
(s) + 3SO
3
(l) Ie
2
(SO
4
)
3
(s) H
o
f
= 443.50 kJ
What is the relation between H and U for a chemical
reaction?
Recall the original definition of H where H U + pV
The expression for dH is:
dH = dU + d(pV)
dH = dU + V dp + p dV
where the second equation above was obtained by
applying the chain rule
If the chemical process occurs under constant volume,
then p dV = 0 and dU = dq
V
. Therefore:
dH
V
= dq
V
+ V dp
The integrated form become:
H
V
= q
V
+ V p = U + V p
24
Under condition of constant pressure the equation
becomes:
H
p
= q
p
+ p V = U + p V
If the chemical process occurs isothermally, and by
assuming the gases involved acting ideally:
d(pV) = d(nRT) = dn RT
where dn refers to the change in the number of moles of
gas that accompanies the chemical reaction
Therefore for isothermal chemical processes, Eqn. 24 and
25 can be written as
H = U + RTn
For Eqn. 26, pressure and volume are not constrained to
be constant
25
26
We can use an idea siniIai lo Hesss Iav lo deleinine
the change in the state function for a process that occurs
in different temperature
The heat change due to the changes of temperature, H
T
is the summation of the following steps:
1. The heat, q, needed to bring the reactants to the
temperature specified by data (usually 298 K)
2. The heat of reaction, H , at that temperature (which can
be determined from tabulated data)
3. The heat, q, needed to bring the products back to the
desired reaction temperature
Step 1: H
1
= q
p
= PcT
It is combined heat capacity of all of the reactants, which must
be included stoichiometrically
Changing Temperature
Step 2: H
2
= H
o
rxn
Evaluate the H for the reaction at 298 K by using products
minusreactants approach
Step 3: H
3
= q
p
= PcT
It is the combined heat capacity of all of the products and must
be included stoichiometrically
Hence, H
T
= H
1
+ H
2
+ H
3