w = PV
The Four Laws of Thermodynamics
force
Change in distance
A. Zeroth Law or the Law of Thermal Equilibrium
If two separate systems are in thermal equilibrium with
a 3rd system, then they are also in thermal equilibrium with
each other.
The isolated system in the figure contains n moles of gas
and is acted upon an external pressure P. When there is
contraction, V is (+) thus W is (+); work in done TO
the system. When expansion occurs, V is (-) thus W is
also (-); work is done BY the system.
If A = C and B = C, Then A = B.
What is Thermal equilibrium?
- no net change in the amount of thermal energy.
- Two systems have the same temperature.
- The basis of thermometer measurements.
B. First Law or the Law of Conservation of Energy
A change in the internal energy of a system is equal to the
sum of the amount of heat energy supplied to or removed
from the system and the work done on or by the system.
U = f(q,w)
U = q + w
What is q?
- It is the heat energy transferred from or by the system
- Heat going out of the system is (-)
- Heat going into the system is (+)
- It is a function of temperature(T) and entropy(S)
What is Internal Energy (U)?
- It is the total energy contained in a system such as a
molecule or any other substance.
- It excludes external kinetic energy (if the system is
moving) or potential energy (of the system as a whole).
- Cannot be directly measured but can be calculated
from changes in heat and work.
- measured in energy per amount of substance (kJ/kg or
kJ/mol)
Ex. 1kg coal has ~20MJ/kg or 10,000Btu/lb
1lb of 235U = 37 GBtu
1 British thermal unit = 1055 J
1 Btu = 1oF increase in 1lb of water
For reactions at constant T, P, and work is being done
by the system:
U = TS PV
Work (kinetic energy)
Heat (potential energy)
q = f(T,S)
q = TS + ST
At constant temperature:
q = TS
q = heating:: w = expansion
w = compression:: q = cooling (or decrease in S)
What is w?
- w = Work done to or by the system
- Work done by the system is (-)
- Work done to the system is (+)
- It is a function of pressure(P) and volume(V)
C. Second Law or the Law of Entropy
w = f(P,V)
w = PV + VP
At constant pressure:
The total entropy of an isolated thermodynamic system
always increases over time, approaching a maximum
value (S).
P
P
The Law of Conservation of Energy holds true because
in a system with a constant internal energy, a change in
the amount of heat energy must be accompanied by an
appropriate change in the work done by the system, and
vice versa.
15 L
10 L
5L
10 L
What is entropy(S)?
- It is a measure of disorder or randomness in a system
- It is the amount of thermal energy that is not available
for work (it is impossible to convert all heat into work).
- It is measured in energy per kelvin (J/K)
- The entropy of a chemical reaction is calculated from:
q = TS + ST
at constant temperature:
q = TS
Thus S = q/T
Srxn = Sproduct - Sreactants
S > 0 spontaneous reaction
S < 0 non-spontaneous reaction
S = 0 reaction is at equilibrium
What is enthalpy (H)?
- It is the total amount of energy that is available for
non-mechanical (heat) work.
- It is measured in energy per amount of substance
(kJ/kg or kJ/mol)
- It is equal to the sum of the internal energy of the
system, U, and the product of pressure, and volume.
H = U + PV
H = U + (PV)
H = q - w + PV + VP
At constant pressure:
H = q PV +PV
H = q
H < 0 exothermic reactions
H > 0 endothermic reactions
H = 0 no heat exchange
What is Gibbs Free Energy (G)?
- It is a measure of the tendency of reactions to occur.
- It is measured in energy per amount of substance
(kJ/kg or kJ/mol)
G = H - TS
G < 0 spontaneous
G > 0 non-spontaneous
A more positive S will contribute to the negativity of G;
thus a more spontaneous reaction.
D. Third Law or Law of Absolute Zero
The entropy of a system approaches zero but never
reaches zero. It is almost zero in a perfect, pure crystal.
An implication of the Third Law is that it is practically
impossible to reach absolute zero using finite amount of
steps in a finite amount of time. However, the third law
provides. However, the Law of Absolute Zero provides the
relationships of thermodynamic parameters and the
responses of certain materials in ultra-low temperatures.
