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The First law

Dr. F. E. Hernndez
Sign convention!
Work & heat
Equivalent ways of
changing the system
internal energy
System Surrounding
Energy
System Surrounding
Energy
w>0, q>0
w<0, q<0
dU = w + q
Work
Expansion work
P
in
> P
ext
}
=
=
=
f
V
Vi
Ext
dV P w
A
A
Fdz dw
Fdz dw
P = F/A
...
...
+ =
+ + + =
HdM dz dV P dw
dw dw dw dw
Ext T
Mag El Epx T
c
Note
2
Pressure-Volume Work
The work of expansion when a piston moves inside a
cylinder is an example of pressure-volume work. We
can show that pressure-volume work is related to the
standard definition of a force operating through a distance.

ow = Fdx =
F
A
Adx = PdV
dx
A
It is important that we define the
work in this form since it depends
on the path. Lets consider two
paths:
1. Reversible (very slow, equilibrium)
2. Irreversible (fast, sudden jump)
3
Reversible Work of Expansion
For the reversible path we will consider a very slow process
where the forces are balanced on either side of the piston
as it expands. Since the pressure on the inside and outside
are evenly balanced, the system in equilibrium and we can
apply the ideal gas law at all times, P = nRT/V.

ow = w = PdV
V
1
V
2
=
nRT
V
dV
V
1
V
2
= nRT
dV
V
V
1
V
2
= nRT ln
V
2
V
1
dx
A
Note that temperature is held constant
for this path. Therefore, a reversible
path is also called an isothermal path.
4
Irreversible Work of Expansion
For the irreversible path the expansion is very fast and the
external pressure is a constant. In this case we no longer
treat P as a variable (as we did for the reversible) case and
we call it P
ext
.

ow = w = P
ext
dV
V
1
V
2
= P
ext
dV
V
1
V
2
= P
ext
V
2
V
1
= P
ext
AV
dx
A
P
ext
must be a smaller pressure
than the starting pressure. Since
the forces are not balanced, less
work is obtained for the irreversible
expansion than for the reversible
expansion.
5
P
Ext
= 0 w = 0
P
Ext
= const. w = -P
Ext
AV

P
Ext
= P
in

Rev
Reversible expansion It can be reverse at any time by
an infinitesimal modification
T
1
= T
2
T
1
T
2
+

dT

dT
Thermal oq
P
in
= P
Ext
P
in
P
Ext
+ dP

dP
ow Mechanical
dx<<1
PV=nRT
Ideal gas
}
=
f
i
V
V
in
dV P w
}
=
f
i
V
V
in
dV P w
i
f
V
V
V
V
nRT w
dV
V
nRT
w
f
i
ln =
=
}
w
Rev
> w
Irrev
6
Isothermal Processes
For an ideal gas the internal energy is the kinetic energy. There is
no potential energy for an ideal gas so this must be true.
Therefore, For an isothermal process T
2
= T
1
= constant so



The internal energy change is always zero for an isothermal
process. If we return to the first law we see that



The system absorbs heat from the surroundings with an energy
equal to the work done.
U =
3
2
nRT , U
m
=
3
2
RT
AU = U
2
U
1
=
3
2
nRT
2

3
2
nRT
1
= 0
AU = w + q = 0
q = w
7
Isochoric and Isobaric Processes
Isochoric means constant volume. The red line in the preceeding
figures is a constant volume process. In such a process w = 0
since dV = 0 (Recall that ow = -PdV).
Therefore, AU = q
V
for an isochoric process. The V subscript
means that V is held constant. Isobaric means constant pressure.
In a constant pressure expansion such as we saw in the preceeding
frames we know how to calculate the work, w = -P
ext
AV.
Moreover, we know that AU for the isochoric process is -q
V
. Since
the end point of the isochor and isobar is the same as that for the
isotherm, we know that overall AU = 0.
Therefore, q
P
= q
V
+ P
ext
AV.
The system absorbs heat from the surroundings with an energy
equal to the work done.
8
Heat
dU = w
Exp
+ w
i
+ q
w
Exp
=0

V = (Const.)
w
i
=0
dU = dq AU = q
V
q
V
=C
cal
AT

Heat capacity
T C U
dT C dU
T
U
C
V
T
T
V
U
U
V
V
f
i
f
i
A = A
=
|
.
|

\
|
c
c
=
} }
q
V
=C
V
AT
V=Const
Ci=nCi
Extensive!
The measurement of heat
We must carefully distinguish between heat and temperature.
When we add heat to the system its temperature increases.
We can use measurement of the temperature to determine
how much heat has been added. However, we need to know
the heat capacity of the system in order to do this.



The heat capacity is called C. If we perform a heat exchange
at constant volume then we designate the heat capacity as C
V
.
If the process occurs at constant pressure we call the heat
capacity C
P
.
Heat capacity=
Heat supplied
Temperaturerise
C
V,P
=
q
V,P
AT
Calorimetry
The science of heat measurement is called calorimetry.
A calorimeter consists of a container in a heat bath.
A physical or chemical process occurs in the container and
heat is added or removed from the heat bath. The
temperature increases or decreases as result. By knowing
the heat capacity of the bath we can measure the amount
of heat that has been added or removed from the system.
Energy in the
form of heat
flows into the bath.
Calorimetry
In the studies of biological systems there are two important
types of calorimetry.
1. Differential scanning calorimetry (DSC)
2. Isothermal titration calorimetry (ITC)

In DSC the temperature is increased at a constant heating
rate and the heat capacity is measured. DSC is used for
determining the parameters associated with phase transitions
e.g. protein unfolding, denaturation, DNA hybridization etc.

In ITC the temperature is held constant while one component
is added to another. The heat of interaction (e.g. binding) is
measured using this method. ITC is widely used to determine
the enthalpy of binding, e.g. for protein-protein and
protein-drug interactions among other types of biological
applications.

Molar and Specific Heat
Capacities
We use molar heat capacities for pure substances. As the
name implies the units are J/mol-K for the molar heat
capacity. We write the molar heat capacity at constant
volume as C
V,m
.

For mixtures we cannot use a molar heat capacity and so
we use the specific heat capacity, which is the heat capacity
per gram of material with units of J/g-K.
Enthalpy
Appears naturally when
P=Const. and V changes
H = U + PV
Extensive!
( )
P
dq dH
VdP dq dH
VdP PdV PdV dq dH
VdP PdV dw dq dH
VdP PdV dU dH
PV d dU dH
=
+ =
+ + =
+ + + =
+ + =
+ =
dU
dw
P=Const.
Relation between AH and AU
AH = AU + A(PV)
For an isothermal change
of an ideal gas (PV=nRT)
AH = AU + A(nRT)
Where An=n(g)
P
-n(g)
R
For liquids and solids
AV0
AH AU
Calculating the
internal energy change
We have seen that the internal energy depends only on
temperature. For example, for a change of pressure
(and temperature) at constant volume we saw that AU = q
V

since the work is zero for a constant volume process.
Thus, at constant volume:


But, in fact when we consider the origin of the internal energy
in the kinetic theory of gases we realize that:


and therefore:
AU = q
V
= C
V
AT
AU =
3
2
nRAT = C
V
AT
C
V
=
3
2
nR and C
V,m
=
3
2
R
The heat capacity
at constant pressure
For a constant pressure step we saw in the last lecture that:


By analogy with the constant volume process:

and therefore:
q
P
= q
V
+ PAV
q
P
= C
P
AT
C
P
AT = C
V
AT + PAV
C
P
AT = C
V
AT + nRAT
C
P
= C
V
+ nR
so that C
P
=
5
2
nR and C
P,m
=
5
2
R
Definition of the enthalpy
Based on these considerations we can see that there is a
new state function, the energy at constant pressure.
This state function is known as the enthalpy H. The enthalpy
change is:

and we can rewrite the relationship from the previous slide as:


We have also defined the relationship between the internal
energy and the enthalpy. The PAV term represents the work
of expansion (or compression) done against the atmosphere
during a chemical reaction. We use enthalpy instead of
internal energy under normal conditions because it includes
this work automatically.
AH = AU + PAV
AH = q
P
= C
P
AT
Variations of the enthalpy with T
T C H
dT C dH
T
H
C
P
T
T
P
H
H
P
P
f
i
f
i
A = A
=
|
.
|

\
|
c
c
=
} }
q
P
=C
P
AT
P=Const
Ci=nCi
Extensive!
Until this point
C
P
C
P
(T)
2
,
T
c
bT a C
m P
+ + =
( ) ( )
(

|
|
.
|

\
|
+ =
|
.
|

\
|
+ + = =
} }
1 2
2
1
2
2 1 2
2
,
1 1
2
1 2
2
1
2
1
T T
c T T
b
T T a H H
dT
T
c
bT a dH dT C dH
T T
H
H
T
T
m P
T
T
Heat Capacity for
a Diatomic Molecule
For a diatomic molecule there is contribution from rotations
as well as translations. This means that as heat is added to
the system the rotational levels can be populated in addition
to an increase in molecular speed. The kinetic theory of
gases considers only the speed. An approximate rule is that
we obtain a contribution to the heat capacity, C
V
of 1/2nR for
each degree of freedom. We saw that for a monatomic gas
the heat capacity was C
V
= 3/2nR. A diatomic gas has two
rotational degrees of freedom and so the heat capacity is
approximately C
V
= 5/2nR. What does this say about C
P
?
Well, the relationship between C
P
and C
V
holds for all gases
so C
P
= 7/2nR for a diatomic ideal gas.