CE304, Spring 2015

Lecture 2

Review of the 1st Law and other Basic Concepts (chapter 2 in SVNA)
Overview:

Definition of internal energy

The first law: Energy is conserved

Energy balances for closed systems

State variables and the concept of thermodynamic states

The phase rule

Reversible processes

Enthalpy and heat capacity

Mass and energy balances for open systems

In the 1840s James Prescott Joule conducted a series of experiments that led to the realization
that work and heat are, in some senses, equivalent. He was among the first to realize that both are
forms of energy, and that total energy (not work or heat alone) is conserved. These experiments
primarily consisted of very precise measurements of the increase in temperature of a fluid when
work was done on it. The original temperature could be restored by allowing heat to flow from
the fluid to a colder object.
Internal energy:
When we add heat to, or do work on, a substance, we increase its total energy. While this
increase may result in changes in kinetic energy, gravitational potential energy, etc., it most often
results in changes in internal energy of the substance. This increase in internal energy is reflected
in an increase in temperature or some other change in the state of the system. From a
macroscopic point of view, this is energy stored within the material that can later be recovered as
heat transferred to a cooler object. Microscopically, this energy is stored in the motions of the
atoms and molecules that make up the material and in the potential energy of the interactions
between them. In classical thermodynamics, absolute values of internal energy are not known,
only relative values, which are all that are required for thermodynamic analysis anyway.
The First Law: Energy is Conserved
Although energy assumes many forms, the total quantity of energy is constant, and when energy
disappears in one form it appears simultaneously in other forms.
You have already made extensive use of the first law of thermodynamics in CE212. It is the basis
for all energy balances, in the same way that mass conservation is the basis of all mass balances.

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Lecture 2

We usually analyze problems in thermodynamics by dividing the universe into the system (the
part we are explicitly studying) and the surroundings (everything else).

The System
(the part of the universe
were looking at)
The Surroundings
(Everything Else)

Any changes in the energy of the system must be accompanied by changes in the energy of the
surroundings. That is
(Energy of the System) + (Energy of the Surroundings) = 0

Energy Balances for Closed Systems:

If our system is closed (no mass flows across its boundaries) then energy can only enter or leave
the system as heat or as work, and we have
(Energy of the System) = Q + W
Where Q is energy transferred from the surroundings to the system as heat, and W is energy
transferred from the surroundings to the system as work (work done on the system by the
surroundings). This implies that
(Energy of the Surroundings) = -Q - W
The sign convention for Q and W used here is the one used in SVNA, but is not universal. You
should always be sure you understand which way energy is flowing and not just rely on the sign
in the equations to get it right.
If all energy transferred into the system goes to increase the internal energy of the system (as
opposed to increasing its kinetic or potential energy by changing its overall position or velocity),
then we have
Ut = Q + W
where Ut is the total internal energy of the system.

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Lecture 2

For infinitesimally small (differential) changes, this is

dUt = dQ + dW
The quantity Ut is an extensive quantity - it is the total internal energy of the system which, if the
system is homogeneous, is proportional to the total amount of matter in the system.
Homogeneous means "the same throughout" - at every point within the system the properties
(temperature, pressure, density, composition, etc.) are the same as at every other point.
If the system is homogeneous, then we can define intensive properties like the internal energy
per mole or per mass
U = Ut/n = internal energy per mole = total internal energy divided by the number of moles,
often called molar internal energy
U = Ut/m = internal energy per mass = total internal energy divided by the total mass, often
called specific internal energy
Then, for a homogeneous closed system containing n moles of material, we can write
(nU) = nU = Q + W
d(nU) = ndU = dQ + dW
Often, we simply write thermodynamic equations for a representative amount of a homogeneous
material, in which case, we would write (for one mole of material, for example)
U = Q + W
dU = dQ + dW
This last expression, in particular, allows us to keep track of the molar (or specific) internal
energy of a substance and compute changes in it by computing the amount of work done on it by
its surroundings and the amount of heat that flows to it from its surroundings. By observing how
its temperature and other properties change as its internal energy changes, we can also relate
changes in internal energy (a property of the substance that cannot be directly measured) to
changes in its other properties (like temperature, density, etc.) that are observable.
Thermodynamic State and State Properties
At a given thermodynamic state, a homogenous system always has the same thermodynamic
properties. For a homogeneous pure substance, fixing two properties (i.e. temperature and
pressure or temperature and density or density and pressure) fixes all of its other thermodynamic
properties (temperature, pressure, density, internal energy, etc.). For more complex systems,
more than 2 thermodynamic properties may have to be specified to specify the state of the
system, but once the required number is specified, the thermodynamic state of the system is fixed
and all other thermodynamic properties are also fixed.

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State functions depend only on the thermodynamic state of the system and do not depend on the
path by which the system arrived at that state. Internal energy is a state function.
Q and W are not state functions. They do not represent properties of the system, but represent
interactions of the system with its surroundings. As such, they depend on the path. The system
can get from one state to another through different paths, where by different paths we mean
through different interactions with its surroundings. If two paths move the system between the
same two states (they cause the same change in the state of the system) then the sum Q + W will
be the same for both paths, because the change in internal energy must be the same. However, Q
and W, individually, will be different for the two paths.
For example, suppose I have some water at a temperature of 280 K and a pressure of 1
atmosphere. Fixing the temperature and pressure specifies the state of the system. I could stir the
water violently until its temperature increased to 300 K (still at 1 atmosphere) while keeping it
thermally insulated. In this case, Q would be zero, and we would have U = W. Alternatively, I
could heat the water from 280 K to 300K by sitting the (non-insulated) beaker on a warm
surface. In this case, no work would be done on the water (W = 0), and we would have U = Q.
Both methods of heating the water result in the same change in the state of the water (they go
from the same initial thermodynamic state to the same final thermodynamic state), so U is the
same in both cases. However, Q and W are different for the two cases.
Reversible Processes
In thermodynamic analyses, we often make use of the idealized concept of a reversible process.
This is similar to the way that we use a lot of frictionless processes in mechanics (and freshman
physics), even though such a process can only be approximately realized in a real system.
A reversible process is one whose direction can be changed at any point by infinitesimal changes
in external conditions
This means there must be no friction, no inertia (so it must happen infinitely slowly), no heat
transfer through finite temperature differences, and so on.
A reversible process

Is frictionless

Is never more than infinitesimally away from equilibrium

Goes through a set of equilibrium states

Is driven by infinitesimally small force or temperature imbalances

Can be reversed at any point by an infinitesimal change in external conditions

When reversed, retraces its original path back to the original state of the system

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Lecture 2

Constant Volume processes, Constant Pressure processes, and Enthalpy

For a homogeneous, closed system containing n moles of a substance, the energy balance was (in
differential form)
d(nU) = dQ + dW
For a mechanically-reversible process on a closed-system, the work term is
dW = -PdVt = -Pd(nV) = -nPdV
So, for a constant volume process, the work is zero and we have
dQ = n dU (at constant V)
or, in integral form
Q = nU (at constant V)
At constant pressure, the energy balance becomes
d(nU) = dQ - nPdV (at constant pressure)
or
dQ = n(dU + PdV) = nd(U + PV) (at constant pressure)
This motivates the definition of enthalpy as H = U + PV, so that at constant pressure dQ = n(dH),
just as at constant volume dQ = n(dU).
Note that even though Q is not a state function, H is defined in terms of U, P, and V, which are
state functions, and therefore H is a state function as well.
See example 2.8 in SVNA.
Heat Capacity
Although U and H are state functions, they are not directly observable. We must infer changes in
U, H, and other such quantities from measured changes in other observable state functions, such
as temperature, pressure, and volume. Thus, we define relationships between these observable
and non-observable (but very useful) quantities. The first of these is heat capacity, which relates
changes in internal energy to changes in temperature.
The constant volume heat capacity is defined as
dU
Cv

dT V

For a constant volume process, we can then write

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dU = CvdT (at constant V)

Or, integrating over a finite change in temperature
T2

U Cv dT (at constant V)
T1

For a mechanically reversible constant-volume process, we then have

T2

Q nU n Cv dT (for a mechanically reversible, constant volume process)

T1

Likewise, we define the heat capacity at constant pressure as

dH
Cp

dT P

Then, for a constant pressure process on a fixed amount of a homogeneous substance, we have
dH = CpdT (at constant P)
and for finite temperature changes
T2

H C p dT (at constant P)
T1

And finally, for a mechanically reversible, constant pressure process, this tells us that
T2

Q nH n C p dT (for a mechanically reversible, constant pressure process)

T1

See example 2.9 in SVNA

Mass and Energy Balances for Open Systems

An open system is one in which mass, as well as energy, crosses the system boundaries. For an
open system, energy is carried in and out of the system with the mass that enters and leaves the
system, as well. In general, we can write a mass balance on a system as
accumulation = in - out

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Short of nuclear reactions, we cannot have a generation term in a mass balance (mass is
conserved). The same is true for a mole balance in a non-reacting system, but of course in a
reacting system we can have a change in the total number of moles due to reaction (leading to a
generation term in the balance equation).
The total mass balance on a fixed control volume with streams entering and leaving it can be
written in SVNA's notation as
dmcv
m fs 0
dt

Where the first term is the time derivative of the total mass in the control volume (accumulation)
and the second term is the difference between the total inflow and outflow (out - in) in the
various streams. This should be very simple compared to things done last semester in CE 212, so
don't let it seem harder than it really is!
Similarly, the energy balance can be written as
d mU cv
dt

H 1 2 u 2 zg m

Q W
fs

where U is the internal energy per unit mass (specific internal energy) within the (homogeneous)
control volume. H is the specific enthalpy of each inflow and outflow stream, u is the average
flow velocity of each inlet and outlet stream, and z is the elevation of each inlet and outlet
stream. In many, many cases, kinetic energy and gravitational potential energy can be neglected,
and this becomes simply
d mU cv
dt

mH fs Q W (when kinetic and potential energy changes are negligible)

Likewise, there will be cases where energy of configuration (compression of a spring, stretching
of a piece of elastomeric material), electromagnetic energy, surface energy, and other forms of
energy not shown in the forms of the equation above may need to be included.
We are often interested in systems at steady state, in which case the time derivative is zero, and
we have simply
mH fs Q W (at steady-state AND when kinetic and potential energy changes are negligible)

There are many possible variations on this energy balance, and one must carefully assess, in a
given problem which form should be used (which terms should be included).
Example 2.13 in SVNA
Example 2.15 in SVNA

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Lecture 2

Summary:
After completing your study of this set of lecture notes and the associated material in chapter 2
of SVNA, you should be able to:

Define internal energy and use it in process calculations

State and apply the first law of thermodynamics and determine what sign conventions are
being used in it

Write and apply energy balances for closed systems

Understand the concept of a thermodynamic state and the difference between state
variables like temperature, pressure, or molar volume and path-dependent variables like
heat or work

Understand what is formally required for a process to be fully reversible or mechanically

reversible; know that no real process can exactly satisfy these criteria, but may
approximate them

Understand that changes in state variables in going from one thermodynamic state to
another will be the same for a real process as for a hypothetical reversible process
connecting the same states

Define and use enthalpy, constant volume heat capacity, and constant pressure heat
capacity

Write and apply material and energy balances for open systems, for both time-dependent
and steady-state processes

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