Professional Documents
Culture Documents
Lecture 9
NC State University
Thermodynamics
NC State University
The Third Law of Thermodynamics
The third law of thermodynamics states that every substance
has a positive entropy, but at zero Kelvin the entropy is
zero for a perfectly crystalline substance. The third law
introduces a numerical scale for the entropy. Stated
succinctly:
Liquid
Solid
Liquid
Solid
Free Energy
NC State University
Free Energy at Constant T and V
Starting with the First Law
dU = dw + dq
At constant temperature and volume we have dw = 0 and
dU = dq
Recall that dS dq/T so we have
dU TdS
which leads to
dU - TdS 0
Since T and V are constant we can write this as
d(U - TS) 0
The quantity in parentheses is a measure of the spontaneity
of the system that depends on known state functions.
Definition of Helmholtz Free Energy
We define a new state function:
A = U -TS such that dA 0.
We call A the Helmholtz free energy.
At constant T and V the Helmholtz free energy will decrease
until all possible spontaneous processes have occurred. At
that point the system will be in equilibrium.
The condition for equilibrium is dA = 0.
A
time
Definition of Helmholtz Free Energy
Expressing the change in the Helmholtz free energy we have
A = U – TS
for an isothermal change from one state to another.
The condition for spontaneous change is that A is less
than zero and the condition for equilibrium is that A = 0.
We write
A = U – TS 0 (at constant T and V)
If A is greater than zero a process is not spontaneous.
It can occur if work is done on the system, however. The
Helmholtz free energy has an important physical interpretation.
Noting the qrev = TS we have
A = U – qrev
According to the first law U – qrev = wrev so
A = wrev (reversible, isothermal)
A represents the maximum amount of reversible work that
can be extracted from the system.
Definition of Gibbs Free Energy
Most reactions occur at constant pressure rather than
constant volume.
Using the facts that dqrev TdS and dwrev = -PdV we have:
dU TdS – PdV
which can be written dU - TdS + PdV 0.
The = sign applies to an equilibrium condition and
the < sign means that the process is spontaneous. Therefore:
d(U - TS + PV) 0 (at constant T and P)
We define a state function G = U + PV – TS = H – TS.
Thus, dG 0 (at constant T and P)
The quantity G is called the Gibb's free energy.
In a system at constant T and P, the Gibb's energy will
decrease as the result of spontaneous processes until
the system reaches equilibrium, where dG = 0.
Comparing Gibbs and Helmholtz
The quantity G is called the Gibb's free energy. In a system
at constant T and P, the Gibb's energy will decrease as the
result of spontaneous processes until the system reaches
equilibrium, where dG = 0.
Comparing the Helmholtz and Gibb's free energies we see
that A(V,T) and G(P,T) are completely analogous except
that A is valid at constant V and G is valid at constant P.
We can see that
G = A + PV
which is exactly analogous to
H = U + PV
the relationship between enthalpy and internal energy.
For chemical processes we see that
G = H – TS 0 (at constant T and P)
A = U – TS 0 (at constant T and V)
Conditions for Spontaneity
We will not use the Helmholtz free energy to describe
chemical processes. It is an important concept in the
derivation of the Gibbs energy. However, from this point
we will consider the implications of the Gibbs energy for
physical and chemical processes.
H S Description of process
>0 >0 Endothermic, spontaneous for T > H/S
<0 <0 Exothermic, spontaneous for T < H/S
<0 >0 Exothermic, spontaneous for all T
>0 >0
<0 Never spontaneous
Gibbs energy for a phase change
For a phase transition the two phases are in equilibrium.
Therefore, G = 0 for a phase transition.
For example, for water liquid and vapor are in equilibrium
at 373.15 K (at 1 atm of pressure). We can write
vapGm = Gm H2O(g) – Gm H2O(l)
where we have expressed G as a molar free energy.
From the definition of free energy we have
vapGm = vapHm – TvapSm
The magnitude of the molar enthalpy of vaporization is
40.7 kJ/mol and that of the entropy is 108.9 J/mol-K.
Thus,
vapG = 40.65 kJ mol – 1 – 373.15 K 108.9 J K – 1 mol – 1 = 0
Gibbs energy for a phase change
However, if we were to calculate the free energy of
vaporization at 372.15 K we would find that it is +1.1 kJ/mol
so vaporization is not spontaneous at that temperature.
If we consider the free energy of vaporization at 374.15 K
it is -1.08 kJ/mol and so the process is spontaneous (G < 0).
State Function Summary
At this point we summarize the state functions that we have
developed:
U (internal energy)
H = U + PV (enthalpy)
S (entropy)
A = U - TS (Helmholtz free energy)
G = U + PV - TS = H - TS (Gibbs free energy)
dH = dU + PdV + VdP
dA = dU - TdS - SdT
dG = dH - TdS - SdT
The internal energy expressed
in terms of its natural variables
We can use the combination of the first and second laws to
derive an expression for the internal energy in terms of its
natural variables. If we consider a reversible process:
dU = dq + dw
dw = -PdV (definition of work)
dq = TdS (second law rearranged)
Therefore, dU = TdS - PdV
G = VdP
P1
Gm = RT dP = RT ln P2
P1 P P1
Note that we have expressed G as a molar quantity Gm = G/n.
The variation of the Gibbs
energy with pressure
We can use the above expression to indicate the
free energy at some pressure P relative to the pressure
of the standard state P = 1 bar.
Gm T = G 0 T + RT ln P
1 bar
G0(T) is the standard molar Gibb’s free energy for a gas.
As discussed above the standard molar Gibb’s free energy
is the free energy of one mole of the gas at 1 bar of pressure.
The Gibb’s free energy increases logarithmically with pressure.
This is entirely an entropic effect.
Note that the 1 bar can be omitted since we can write:
RT ln P = RT ln P – RT ln 1 = RT ln P
1 bar
The pressure dependence of G for
liquids and solids
If we are dealing with a liquid or a solid the molar volume
is more or less a constant as a function of pressure.
Actually, it depends on the isothermal compressibility,
k = -1/V(V/P)T, but k is very small. It is a number of the
order 10-4 atm-1 for liquids and 10-6 atm-1 for solids. We
have discussed the fact that the density of liquids is
not strongly affected by pressure. The small value of k
is another way of saying the same thing.
For our purposes we can treat the volume as a constant
and we obtain
Gm T = G 0 T + Vm P – 1
Systems with more than one
component
Up to this point we have derived state functions for pure
systems. (The one exception is the entropy of mixing).
However, in order for a chemical change to occur we must
have more than one component present. We need generalize
the methods to account for the presence of more than one
type of molecule. In the introduction we stated that we would
do this using a quantity called the chemical potential. The
chemical potential is nothing more than the molar Gibbs
free energy of a particular component. Formally we write it
this way:
Rate of change of G as number of
i = G moles of i changes with all other
ni T,P, j i variables held constant.
Example: a gas phase reaction
Let’s consider a gas phase reaction as an example. We will
use a textbook example:
N2O4 (g) = 2 NO2 (g)
We know how to write the equilibrium constant for this reaction.
2
P NO 2
K=
PN 2O4
At constant T and P we will write the total Gibbs energy as:
rxnG = dG
dn T,P
This is rxnG but it is not rxnGo! Note that we will use rxnG
and G interchangably.
If we now apply the pressure dependence for one component,
Gm T = G 0 T + RT ln P
1 bar
to a multicomponent system:
Pi
i T = 0i T + RT ln
1 bar
These two expressions are essentially identical. The
chemical potential, i, is nothing more than a molar free energy.
Application of definitions to the
chemical reaction
We can write the Gibbs energy as:
G = 2NO2 – N2O4
and use the chemical potentials:
NO 2= 0NO 2 + RT ln PNO 2
N 2O4= 0N2O4 + RT ln PN2O4
PN2O4
Note the significance of G and Go
The change G is the change in the Gibbs energy function.
It has three possible ranges of value:
G < 0 (process is spontaneous)
G = 0 (system is at equilibrium)
G > 0 (reverse process is spontaneous)
PN2O4
Temperature dependence of Go
The van’t Hoff equation
We use two facts that we have derived to determine the
temperature dependence of the free energy.
G 0 = –RT ln(K)
G 0 = H 0 – TS 0
ln(K) = – H 0
+ S 0
RT R
ln(K 2) – ln(K 1) = H 0
1 – 1
R T1 T2
Slope = -Ho/R
Note: Ho > 0
Slope = -Ho/R
Note: Ho < 0
Initial 0
Delta -x 2x +x
Final
To solve a gas phase problem you need to know
whether the pressure can change or not. If it is
fixed, then Ptot has a value that does not change.
The mole fractions are,
N2O4
P = 1 – G = 1 – G
0 0
Vm M –M
r d r gr
Example: the formation of diamond
Plugging the values we find:
0 = G 0 + Vm P – 1
P=1– G 0
=1– G 0
Vm M –M
r d r gr
=1– 2900 J/mol
0.012 kg/mol 1 – 1
3510 2260
9
= 1.5 x 10 Pa = 15000 bar