Chapter 02

Fuel Cell Thermodynamics

Lecture Notes
Dr. Sammia Shahid
What is Thermodynamics?
Thermo

means heat" and Dynamics
relates to "movement"; in essence
thermodynamics studies the movement of
heat energy and how that energy makes
mechanical movement (i.e. does work).
Thermodynamics is a science about the
effects of changes in temperature,
pressure, and volume

and how these
changes effect a physical system.
(e.g. a car engine, an air conditioner)
Thermodynamics
Studies energy changes and the direction of flow of energy usually in a well-defined
part of the universe (the system)
System: part of the universe in which we are interested
Surroundings:

where we make our observations (the universe)
Boundary: separates above two
When Energy flows from a hot object to a
cold object, the energy is called Heat
Heat is the energy that flows from one object to
another due to a temperature difference.
Fast moving atoms with a lot of random motion collide with slower moving
atoms.
As kinetic energy is transferred from the fast moving atoms to the slower
moving atoms, we say that the warmer side gave up heat to the colder side and
that heat was transferred.
Two objects in contact on a microscopic level:
Fast
moving
Slow
moving
What is Temperature?
Temperature is a measurement of the average thermal

energy

of the particles in a substance.
Heat flows due to temperature differences.
No heat is transferred between two objects that are at the
same temperature (i.e. in thermal equilibrium). If two bodies
are in thermal equilibrium with a third body, they are also in
thermal equilibrium with each other. This simple fact is known
as the zeroth law of thermodynamics.
A cup of boiling water is at the same temperature as a gallon
of boiling water, but the gallon of boiling water has more
thermal energy than the cup.
How does Heat flow?

Conduction

the transfer
of heat energy by making
direct contact with the
atoms/molecules of the
hotter object

Convection

the transfer
of heat due to a bulk
movement of matter from
hotter to colder areas

Radiation

energy
transferred by
electromagnetic waves
Conduction

When two objects are in direct contact,
particles in the hotter object are moving
faster and will collide with slower
moving objects in the colder object.

When this happens, heat flows.

Energy is transferred from the hot object
to the cold object.
Convection
Buoyancy forces
cause bulk
movement of the
water.
www.physics.arizona.ed
More examples of Convection
Rising hot air and falling
cool air sets up convection
cells.
Convection Ovens
A fan circulates the air so hot
air is not trapped at the top of
the oven. More cookies can
be baked at one time and all
will cook at the same rate.
Heat Transfer from Radiation

All matter that has thermal energy will emit infrared
electromagnetic radiation.

We can feel this when we put our hands close to a fire.

This type of heat transfer requires no medium.
Electromagnetic radiation travels at the speed of light
through a vacuum.
http://www.newt.com
http://www.charlesandhudson.com
Energy

Definition: the capacity to do WORK

Units are Joules (J) = kg.m
2
/s
2
(from KE=1/2mv
2
)
Work done on a system -

system gains energy (w +ve)
Work done by the system -

system loses energy (w -ve)
Heat absorbed by the system (endothermic) -

system gains energy (q +ve)
Heat released by the system (exothermic) -

system loses energy (q +ve)
SYSTEM TOTAL ENERGY (kinetic plus potential) is the
INTERNAL ENERGY (U sometimes E)
Usually measure CHANGE in internal energy ( U )
U=U
final
U
initial
U is a STATE FUNCTION (independent of path)
Energy

There are three broad concepts of energy:

Kinetic Energy

is the energy associated with an
object by virtue of its motion.

Potential Energy

is the energy an object has by
virtue of its position in a field of force.

Internal Energy

is the sum of the kinetic and
potential energies of the particles making up a
substance.
Energy

Internal Energy

is the energy of the particles
making up a substance.

The total energy of a system is the sum of its
kinetic energy, potential energy, and internal
energy, U.
U E E E
p k tot
+ + =
A system is said to be in thermodynamic equilibrium if it maintains
thermal (uniform temperature), mechanical (uniform pressure),
phase (the mass of two phases, e.g., ice and liquid water, in
equilibrium) and chemical equilibrium.
Equilibrium
Process
Any change from one state to another is called a process. In most of
the processes that we will study, one thermodynamic property is held
constant. Some of these processes are:
Process Property held
constant
isobaric pressure
isothermal temperature
isochoric volume
isentropic entropy
Energy

The Law of Conservation of Energy:

Energy may be converted from one
form to another, but the total quantities
of energy remain constant.
Heat and Work
Heat: transfer of energy that
changes motions of atoms in
the surroundings in a chaotic
manner
Work: transfer of energy that changes
motions of atoms in the surroundings
in a uniform manner
= F x d
Work (W)
Work involves the movement of matter from one
place to another. Examples of Work include:

Pressure Volume Work (Expansion work)

Electrical work

Mechanical work
In Thermodynamics work always involves the
exchange of energy between system and its
surroundings.
Expansion Work
w = F x d Work

= Force x Distance
Energy and Enthalpy
Constant Pressure:
E = q + w
w = work = -PV
q = heat transferred
q = E + PV
q
P

= E + PV
Constant Volume (V = 0): q
V

= E
Energy and Enthalpy
= H
products

-

H
reactants
H
Enthalpy change
or
Heat of reaction (at constant pressure)
q
P

= E + PV =
H = H
final

-

H
initial
Enthalpy is a state function whose
value depends only on the current
state of the system, not on the
path taken to arrive at that state.
Fossil Fuels, Fuel Efficiency, and
Heats of Combustion
CO
2

(g) + 2H
2

O(l) CH
4

(g) + 2O
2

(g)
Laws of Thermodynamics
Zeroth Law:
If two objects are in thermal equilibrium
with a third object, then they are also in
thermal equilibrium with each other.
Thermal equilibrium means an objects temperature,
pressure, and volume are not changing.
A cooling cup of coffee is NOT in
thermal equilibrium with the room.
Zeroth Law
If two cups of coffee are at
thermal equilibrium with the room,
then the two cups are in thermal
equilibrium with each other.
The two cups of coffee have the
same temperature.
If the two cups are put in contact
with each other no heat will flow.
Zeroth Law
First Law of Thermodynamics: The good news!
Energy is Conserved. Energy can not be destroyed.
In an isolated system, the total energy stays the same.
Energy can be converted from one form to another.
Thermal Energy can be converted into another form of
energy!
heat transfer out
heat transfer out
(exothermic),
(exothermic),
-
-
q
q
heat transfer in
heat transfer in
(endothermic), +q
(endothermic), +q
SYSTEM
SYSTEM
SYSTEM
E = q + w
E = q + w
w transfer in
w transfer in
(+w)
(+w)
w transfer out
w transfer out
(
(
-
-
w)
w)
What is Entropy?
Entropy = total disorder of an object/system
Disorder is the sum of the thermal energy plus
the physical disorder.
Entropy always increases with time!
Examples of increasing entropy
Energy flows in one direction

towards a
more disordered state
Entropy
+
Heat, light, ash,
particulates, gases
Direction
Is possible
+
Heat, light, ash,
particulates, gases
Direction
Is impossible
Examples of increasing entropy
Entropy
Spontaneous Process: A process that, once
started, proceeds on its own without a continuous
external influence.
Spontaneous processes are
favored by a decrease in H (negative H).
favored by an increase in S (positive S).
Nonspontaneous processes are
favored by an increase in H (positive H).
favored by a decrease in S (negative S).
Entropy (S): The amount of molecular
randomness in a system.
An Introduction to Free Energy
Gibbs Free Energy Change (G)
Entropy
change
G =
Enthalpy of
reaction
Temperature
(Kelvin)
H S -
T
An Introduction to Free Energy
Gibbs Free Energy Change (G)
G = H S -
T
G < 0

Process is spontaneous
G = 0

Process is at equilibrium
(neither spontaneous nor nonspontaneous)
G > 0

Process is nonspontaneous
The Second Law of Thermodynamics:
(The bad news!)
An isolated system gets more disordered with
time.
Entropy always increases with time.
What does this mean to us?

It is impossible to construct an engine that
converts all its thermal energy into useful work.
The exhaust must be hotter than the incoming
air.

100% efficiency is impossible there must be
some unusable energy because entropy must
increase.

Were going to get old and die

The house is going to need cleaning again!
Why is 100% efficiency theoretically
impossible?

If machine operates in
a cycle, some energy
must be used to reset
the machine.

Parts of machine will
absorb some of the
heat.

Exhaust must be
hotter than incoming
air, due to 2
nd

law.
This hot exhaust
represents wasted
energy.
Second Law of Thermodynamics

Maintenance of complex, dynamic
system requires energy input.

Then, energy conversions lose energy
to universe.

Without more energy input, disorder
(entropy) increases.
Apply to human body

Input of energy

Losses

Energy used to maintain
organization

disorder death.
Apply to environmental system

Fuel cells to power cars

2H
2

(fuel) + O
2

(from air) H
2
O + electricity

Electricity powers car

Technology exists!

Apollo program, Space shuttles

Working cars

Source of H
2

??
The Earths Thermodynamic System
Energy Conversion of Fuels
The combustion process is a chemical reaction whereby fuel is
oxidized and energy is released.
Fuels are usually composed of some compound or mixture containing
carbon, C, and hydrogen, H
2

.
Examples of hydrocarbon fuels are
CH
4

Methane
C
8

H
18

Octane
Coal

Mixture of C, H
2

, S, O
2

, N
2

and non-combustibles
Initially, we shall consider only those reactions that go to completion.
The components prior to the reaction are called reactants and the
components after the reaction are called products.
Heat Engine
A heat engine is a thermodynamic system operating in a thermodynamic
cycle to which net heat is transferred and from which net work is delivered.
The system, or working fluid, undergoes a series of processes that constitute
the heat engine cycle.
The following figure illustrates a steam power plant as a heat engine
operating in a thermodynamic cycle.
Early cars employed three technologies
1.

Steam powered
2.

Electric battery powered
3.

Gasoline and Diesel powered
Stanley Steam Car 1912
Steam Cars

Heavy

Slow to heat up and
start

Required carrying
both fuel and water
http://www.steamcar.net/my-85.html
Steam Engine

Steam Engine

Heat generates steam increasing pressure

Pressurized steam does work driving a piston or shaft

Exhausted steam gets rid of waste heat

Being the cycle over
First electric vehicles (EV)

Edison worked on battery
storage believing that
electricity would power
future cars

In 1900, roughly a third of
all vehicles sold are EVs

EVs were marketed to
women and for urban
areas
Thomas Edison circa 1900
Morrisons 4-horse
power EV with a
range of 50 miles.
Early Gas powered cars
Karl Benz was the
first to commercialize
a gas powered
motorwagon in 1885
Why did EVs and Steamers fade away?

Gasoline and Diesel have high energy
densities

Greatest need for cars and trucks was in
rural areas, therefore long range was
needed.

Steamers too heavy on unpaved roads

Gas powered cars started quickly

Henry Ford perfected the assembly-line,
making his cars the most affordable
Why was gasoline the chosen fuel
source for the automobile?

Gasoline has 1000X the energy as an equal
weight of batteries.

Gasoline has 4.5X more energy per gallon than
liquid hydrogen.

Gasoline has 2X the energy of coal for the same
weight

Gas has slightly less energy per volume as
veggie oil

Gasoline combines with Oxygen when it burns.
The Oxygen is free and does not have to be
carried.
Overall 4-stroke cycle
Area enclosed with the cycle is the proportional to the work
done
Diesel Engine
Diesel Cycle
Isobaric combustion
Fuel injected into hot
air after compression
permits higher
compression ratio
Diesel vs. IC

Diesel achieves higher
compression ratios

gives higher efficiency

Direct fuel injection after
compression

Diesel fuel (~C10
paraffins) is cheaper to
recover from petroleum

More particulates in the
emissions

Better acceleration
(power)

Easier to start up,
particularly in cold
weather

Better emissions control
technology
Internal Combustion vs. External Combustion

Pros of IC

electric starter, so easier
and quick to start up

Cons of IC

By-products of
combustion in exhaust
gases
Pros of EC
Fuel can be anything
Cons of EC
Slow to start
Heat exchanger needed
If steam is the working fluid:
Boiler needed
Water freezes at low
temperatures
External Combustion

the fluid doing the work (working fluid) is
heated externally.
Internal Combustion

the fluid doing the work is heated by
burning a fuel internally inside a cylinder pushing down on a
piston Major Plus
Thermal Efficiency,

th
The thermal efficiency is the index of performance of a work-

producing device or a heat engine and is defined by the ratio of

the net work output (the desired result) to the heat input (the
costs to obtain the desired result).
For a heat engine the desired result is the net work done and
the input is the heat supplied to make the cycle operate. The
thermal efficiency is always less than 1 or less than 100
percent.

th
=
Desired Result
Required Input
Why 100% efficiency is impossible?

At least some of the energy must be passed on
to heat a low-temperature energy sink

This is due to the 2
nd

Law of Thermodynamics

Entropy must increase!

Engine needs to be reset.

Engine parts will absorb some of the heat
energy.
Fuel Cell versus Carnot
Efficiency
Result from Thermodynamics

According to thermodynamics, even
under ideal conditions, a heat engine is
incapable of converting all heat energy
supplied to it into mechanical energy.
Some of the heat is rejected.
Internal Combustion engine

Accepts heat from a source at a high
temperature T
h

Converts part of the energy into mechanical
work

Rejects the remainder to a heat sink at a low
temperature T
c

Greater the temperature difference, greater
the efficiency!!
Efficiency of an internal combustion engine
maximum efficiency of an internal combustion engine is
given by

carnot

= (T
h

T
c

) / T
h
, where
T
h
and T
c

are temperatures of the heat source and heat sink in
degrees Kelvin.
As seen by the above equation, this efficiency cannot exceed
the
Carnot limit!!!
Efficiency of a Fuel Cell
The theoretical efficiency of a fuel cell is given by

fc

= G
0
/H
0
where G
0

is the chemical energy (or Gibbs energy)
and H
0

is the total heat energy or Enthalpy of the
fuel.
NOTE: This efficiency can exceed the Carnot limit
because the electrochemical process of the fuel cell
does not involve conversion of thermal to mechanical
energy!!
Fuel cell powered electric car
With pure hydrogen it has the potential of having 80%
efficiency.
Since hydrogen is difficult to store in a car, a reformer is
needed to convert methanol to hydrogen.
This drops the efficiency to 30-40%
Conversion of electric energy into mechanical work
requires an electric motor and inverter.
Accounting for all these processes ultimately gives an
efficiency of about 24-32%.
Fuel Cell Powered Electric Car
Gasoline powered car
All heat coming out as exhaust or going into
radiator is wasted energy.
Engine uses up lot of energy in turning the various
pumps, fans and generators.
So overall efficiency of an automotive gas engine
is about 20%.