The Enthalpy

Let us consider a control mass undergoing a quasi-

equilibrium constant-pressure process, as shown in Fig.
5.6.
[ specific enthalpy, h, and total enthalpy, H. ]
 The Enthalpy
Isobaric processes (P = const):

dU = Q - PV = Q -(PV)  Q =  U + (PV)

 H  U + PV - the enthalpy
The enthalpy is a state function, because U, P,
and V are state functions. In isobaric processes,
the energy received by a system by heating equals
to the change in enthalpy.
in both cases, Q
isochoric: Q=U does not
depend on the
isobaric: Q=H path from 1 to 2.

Consequence: the energy released (absorbed) in chemical reactions at constant

volume (pressure) depends only on the initial and final states of a system.
f f 
The enthalpy of an ideal gas: H  U  PV  Nk BT  Nk BT    1 Nk BT
(depends on T only) 2 2 
 Heat Capacity

The heat capacity of a system - the amount of energy

Q
transfer due to heating required to produce a unit C
temperature rise in that system T
T
f1 f2 f3
C is NOT a state function (since Q is not a T1+dT
state function) – it depends on the path
between two states of a system  T1
i

V
( isothermic – C = , adiabatic – C = 0 )

C
The specific heat capacity c
m
 CV and CP

 U  the heat capacity at

CV   
Q dU  PdV  T V constant volume
C 
dT dT
 H  the heat capacity at
CP   
 T  P constant pressure

To find CP and CV, we need f (P,V,T) = 0 and U = U (V,T)

f  f 
U  Nk BT
For an ideal gas H    1  Nk BT
2 2 
f f  f 
CV  Nk B  nR CP    1 nR
2 2 2 
# of moles
3 5
For one mole of a CV  R CP  R
monatomic ideal gas: 2 2
The First Law as a Rate Equation
( Dividing the first law equation by δt )
 The Second Law of Thermodynamics

We observe that heat always flows

spontaneously from a warmer object to a cooler
one, although the opposite would not violate the
conservation of energy. This direction of heat
flow is one of the ways of expressing the
second law of thermodynamics:
When objects of different temperatures are brought
into thermal contact, the spontaneous flow of heat
that results is always from the high temperature
object to the low temperature object. Spontaneous
heat flow never proceeds in the reverse direction.
 Heat Engines and the Carnot Cycle
A heat engine is a device that converts heat into
work. A classic example is the steam engine.
Fuel heats the water; the vapor expands and
does work against the piston; the vapor
condenses back
into water again
and the cycle
repeats.
 Heat Engines and the Carnot Cycle

All heat engines have:

• a high-temperature reservoir
• a low-temperature reservoir
• a cyclical engine
These are illustrated
schematically here.
 Heat Engines and the Carnot Cycle

An amount of heat Qh is supplied from the hot

reservoir to the engine during each cycle. Of that
heat, some appears as work, and the rest, Qc, is
given off as waste heat to the cold reservoir.

The efficiency is the fraction of the heat

supplied to the engine that appears as work.
 Heat Engines and the Carnot Cycle
The efficiency can also be written:

In order for the engine to run, there must

be a temperature difference; otherwise
heat will not be transferred.
 Heat Engines and the Carnot Cycle

The maximum-efficiency heat engine is

described in Carnot’s theorem:
If an engine operating between two constant-
temperature reservoirs is to have maximum
efficiency, it must be an engine in which all processes
are reversible. In addition, all reversible engines
operating between the same two temperatures, Tc
and Th, have the same efficiency.
This is an idealization; no real engine can be
perfectly reversible.
 Heat Engines and the Carnot Cycle

If the efficiency depends only on the two

temperatures, the ratio of the temperatures must
be the same as the ratio of the transferred heats.
Therefore, the maximum efficiency of a heat
engine can be written:
 Heat Engines and the Carnot Cycle
The maximum work a heat engine can do is
then:

If the two reservoirs are at the same

temperature, the efficiency is zero; the
smaller the ratio of the cold temperature to
the hot temperature, the closer the efficiency
will be to 1.
 Refrigerators, Air Conditioners, and Heat
Pumps

While heat will flow spontaneously only from a

higher temperature to a lower one, it can be
made to flow the other way if work is done on
the system. Heat pumps all use work to
transfer heat from a cold object to a hot
object.
 Refrigerators, Air Conditioners, and Heat
Pumps
If we compare the
heat engine and the
refrigerator, we see
that the refrigerator
is basically a heat
engine running
backwards – it uses
work to extract heat
from the cold
reservoir (the inside of the refrigerator) and
exhausts to the kitchen. Note that
- more heat is exhausted to the kitchen than is
removed from the refrigerator.
 Refrigerators, Air Conditioners, and Heat
Pumps
An ideal refrigerator would remove the most
heat from the interior while requiring the
smallest amount of work. This ratio is called the
coefficient of performance, COP:

Typical refrigerators have COP values between

2 and 6. Bigger is better!
Refrigerators, Air Conditioners, and Heat
Pumps
An air conditioner is
essentially identical to a
refrigerator; the cold reservoir
is the interior of the house or
other space being cooled, and
the hot reservoir is outdoors.
Exhausting an air conditioner
within the house will result in
the house becoming warmer,
just as keeping the refrigerator
door open will result in the
kitchen becoming warmer.
Refrigerators, Air Conditioners, and Heat
Pumps
Finally, a heat pump is the
same as an air conditioner,
except with the reservoirs
reversed. Heat is removed
from the cold reservoir
outside, and exhausted
into the house, keeping it
warm. Note that the work
the pump does actually
contributes to the desired
result (a warmer house) in
this case.
 Refrigerators, Air Conditioners, and Heat
Pumps
In an ideal heat pump with two operating
temperatures (cold and hot), the Carnot relationship
holds; the work needed to add heat Qh to a room is:

The COP for a heat pump:

 Entropy
A reversible engine has the following relation
between the heat transferred and the reservoir
temperatures:

Rewriting,

This quantity, Q/T, is the same for both reservoirs,

and is defined as the change in entropy.
 Entropy

For this definition to be valid, the heat transfer

must be reversible.
In a reversible heat engine, it can be shown
that the entropy does not change.
 Entropy
A real engine will operate at a lower efficiency
than a reversible engine; this means that less
heat is converted to work. Therefore,

Any irreversible process results in an

increase of entropy.
 Entropy

To generalize:
• The total entropy of the universe increases whenever
an irreversible process occurs.
• The total entropy of the universe is unchanged
whenever a reversible process occurs.
Since all real processes are irreversible, the
entropy of the universe continually increases. If
entropy decreases in a system due to work
being done on it, a greater increase in entropy
occurs outside the system.
 Entropy

As the total entropy of the universe

increases, its ability to do work decreases.
The excess heat exhausted during an
irreversible process cannot be recovered;
doing that would require a decrease in
entropy, which is not possible.
 Order, Disorder, and Entropy
Entropy can be thought of as the increase in
disorder in the universe. In this diagram, the
end state is less ordered than the initial state –
the separation between low and high
temperature areas has been lost.
 Order, Disorder, and Entropy

So if entropy is continually increasing, how is

life possible? How is it that species can evolve
into ever more complex forms? Doesn’t this
violate the second law of thermodynamics?
No – life and increasing complexity can exist
because they use energy to drive their
functioning. The overall entropy of the universe
is still increasing. When a living entity stops
using energy, it dies, and its entropy can
increase rather quickly.