CEIC2000

Thermodynamics - Lecture 2
The First Law
Forms of Energy

School of Chemical Engineering

UNSW Sydney
 Lecture 2 – The first law
1. Forms of energy
2. The first law of thermodynamics
3. Enthalpy

(complement to Moodle lesson or 1st year CHEM PHYS)

Learning outcomes:
State and illustrate by example:
• The first law of thermodynamics- that is the conservation of mass
and energy – and its basic concepts,
• Conversion of energy from one form to another and
• Transfer of energy from the surroundings to the system by heat,
work.

You can check the following resources, if more information needed:

Video on first law,
Felder and Rousseau (Section 7.1),
Smith et al. (Ch. 2, and Section 3.3),
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The First Law of Thermodynamics

Energy cannot be created or destroyed.

You can only change it from one form to

another, or you can only add it to the
system from the surroundings.

DEuniverse = 0
(universe is considered an isolated system)
visit Moodle lesson
3
 Reminder:
In thermodynamic jargon, we often use the term “system” for a closed or
batch process (e.g. a piston cylinder)
“Surroundings” is the space that could be affected by changes within the
"system".
(The universe is the largest “system” we could have!. It will be ignored (not
to be affected by our processes most of the time)
We often use the term “control volume” for open systems or section of
space that we are considering.

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1. Forms of Energy:

- Kinetic and potential energy (Ek and Ep).

- Heat (Q),
- Work (W)

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 Potential Energy (Ep)

Covered in 1st year Physics

Changing the potential energy (Ep) of

an object comes from changing its
location in a force field a such as:
• Gravitational (raising an object from the
ground)
• Electrical (pushing electrons towards a
negative charged plate)
• Winding up a spring/rubber band

Ep = g  z

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Kinetic Energy (Ek)

Covered in 1st year Physics

Changing the kinetic energy of an object (Ek) comes
from changing its velocity.

Ek = u2/2

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Work and heat
Both are forms for the TRANSFER OF ENERGY between the
surrounding and the system.
In closed systems, transfer of energy can only be accomplished by heat
or work.
Heat is the transfer of energy by a temperature gradient (conduction,
convection and radiation)
All other forms of energy transfer is a closed system occur via work
Heat
Heat (Q) - way of adding or removing energy from system by contact
with a hotter or colder body

The walls of container that permit energy transfer as heat are called
diathermic.

Walls that do not permit energy transfer as heat are called adiabatic.

A process that releases heat is called exothermic and a process that

absorbs energy as heat is called endothermic.
Work

Work (W) - all ways of changing the energy of a system other than
adding or removing heat:

Push- pull (pressure) work (piston cylinder)

Electric or magnetic (electric motor)
Chemical Work (combustion)
Surface Work (creating surfaces)
Elastic Work (rubber band, spring)

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Introduction to energy transfer by work

(also refer to online block – Forms of energy)

 Irreversible expansion work (w)

Expansion work is defined as the work done when a

system expands against an opposition pressure.

When a system expands through a volume DV

against a constant external pressure pex, the work
done is:

                                   w = - pex DV

Note: usual sign convention in thermodynamics: w is

negative if energy leaves the system as work, but
positive if energy enters the system 
Justification

Consider a piston of area A moving through

a distance h.
The force F, opposing the expansion is the
constant external pressure pex multiplied
by the area of the piston A (remember
that p = F/A)
The work done here is equal to the
opposing force multiplied by the
distance moved: Now consider the sign:
Work done (w) = F x distance System does work, loses energy,
                        = (pex A) . h and w is expected to be
negative when it expands
                         = pex . hA
(DV is positive)
                         = pex . DV This is why we need the
(by convention) = - pex . DV negative sign
Reversible expansion work
W = -pex DV shows how to get the least expansion work from a system.
What could be the greatest work achieved by change of volume?
This will be when pex is the biggest possible, but cannot be larger than
pressure inside system. So, max work obtained when pex is only
infinitesimally less than the pressure inside.
When the 2 pressures are adjusted continuously during expansion =
state of mechanical equilibrium = reversible expansion = no friction
 Mathematical definition of reversible work
Work = force applied to an object x distance the object moves
x2
W  =  ò Fdx
(Units = Joules = J = N.m) Force = mass x g
= kg x m.s-2 = N
Pressure = Force / Area
x1
= N.m-2
V
F 2
Work = Force x distance
W   =   Fdx   d ( xA)   Pex dV = N.m (also called Joule)
A V1 Or = Pressure x volume
=N.m-2 x m3 = N.m

With Pex being external pressure

for quasi-equilibrium (reversible, i.e. no friction – no loss of energy) expansion in
piston-cylinder, often referred as “PV work”, or “moving-boundary work”  

How would you represent a reversible compression??

Check video here
15
Summing up
 W =-

Reversible Irreversible
(no friction; Pex is continuously changing) Pex = constant = Pfinal

P P
P1 P1

Expansion P2
V
P2
V
V1 V2 V1 V2

 Wrev = - Wirrev = - P2 . DV

P P
P1 P1

Compression P2
V P2
V
V1 V2 V1 V2

 Wrev = - Wirrev = - P1 . DV
Work for Steady State Processes

• Fluid, PV, or flow work is the work done by the system

due to movement of the system’s boundary. (such as
going from liquid to steam) or moving the fluid through
the control volume.

• Shaft work (Ws) is the work done by or on the fluid as it

passes through a piece of equipment (like a turbine).
This can be mechanical or electrical in form. Converting
internal energy into useful work.

• More details in upcoming examples and Lectures 7-10

Calculating reversible work
Question:
Determine the work done when 1.0 mol of Ar(g) confined in a cylinder of
volume 1.0dm3 at 25C expands isothermally and reversibly to 2.0dm3
(enter working here)
Example – Work in Cycle

Consider a given amount of ideal gas in a piston at 50C and 2 bar and
volume V1.
The gas produce work through its expansion (isothermally) to twice its
original volume (V2 = 2 x V1),
The piston is then returned to its original condition (volume and
temperature) through:
1. Pumping back to V1 through an isobaric cooling (step 2)
2. Heating at constant volume back to T1 (step 3).

Demonstrate that the net work is non-zero and therefore work depends on
path.
Ideal gas in a piston at 50C (T1) and 2 bar and volume V1. The gas is expanded
isothermally to twice its original volume (V2 = 2 x V1), then cooled isobarically to V1
(step 2), it is then heated at constant volume back to T1 (step 3).

P
1
W1 to2 = Work provided by system
V1 1
T1 = 50C
P1= 2 bar 2 Work = 0
2
3 T1
V2 =2xV1
T3
T2=T1
W2to3 = Work provided to system
P2

3 W1to2 <0
V
V3=V1 W2to3 >0
T3<T2 |W1to2| > |W2to3|
P3=P2 So the system will have to produce more work than it
will obtain, and will lose energy during this cycle
 Introduction to Internal Energy
It is difficult to determine the absolute value of internal energy, U, but we
can calculate the change of internal energy (U) by determining the
boundary and the energy (heat, work, potential, and kinetic energy)
which flows into and out of the system.

In a bank, “money” could come in and out in various With ∆U = Ufinal – Uinitial
forms, but at the end of the day, the manager needs to
know how much “$$” is in, and how much $$ has
accumulated within the day (=$$ evening - $$morning).
Change in Internal Energy (U) 

Change in internal energy can participate to the following:

• Changing the temperature of a system (heat or cooling)
• Changing the phase of a system (solid to liquid, liquid to gas etc.)
• Changing the molecular arrangement (chemical reaction)
• Changing the atomic structure (atomic fission) by break up of large
atoms
• Combining small atoms into large atoms (nuclear fusion)
 Example of change in Internal Energy (DU)

A system releases 10kJ of energy into the surroundings by doing work

W = - 10 kJ
U1

The Internal Energy of the system decreases by 10kJ

DU = U2 – U1 = -10 kJ

U2

Now consider a system that gain 20 kJ by heat and produces 10 kJ of work.

DU = 20 – 10 = + 10 kJ
2. The First Law of Thermodynamics
The First Law of Thermodynamics

Energy cannot be created or destroyed.

You can only change it from one form to

another, or you can only add it to the
system from the surroundings.

DEuniverse = 0
(universe is considered an isolated system)
Revisit Moodle lesson
Background reading
(Homework)

To demonstrate how energy

form can change form but
total amount remains
constant

= First law of
Thermodynamis

From Smith et al.

First law (energy balance) in closed system
+Q

+W
System Property
DEk = Ek,2 – Ek,1
Surroundings
DEp = Ep,2 – Ep,1
DU = U2 – U1 Boundary

{Change in energy in system} = {energy transferred from surroundings to

system}
DU + DEk+ DEp = Q + W
Most of the time in thermo systems, DEkand DEp are negligible and we can
write:
DU = Q + W
State vs Path Functions
When a system goes from an initial state i to a final state f,
its internal energy has changed from Ui to Uf
U = Uf - Ui

The internal energy of system depends on its state, not

how it arrived to this state. Therefore the internal energy is
called a state function.
For U:
UA = UB

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State vs Path Function
On the other hand, the amount of Work and Heat added or removed
in the process or a series of processes depends on the path that the
system takes to go to the final state.
The work and heat changes depend on its path, not how it arrived the
final state.
Therefore the work and heat are called path functions.

For W:
WA ≠ WB
Intensive vs Extensive

Extensive properties are those related to amount that you have

(mass, internal energy (kJ/kg)). Depend on the size of the system.
They are additive.
Also note that Q, W, U (all energy) are all extensive and given in
Joules (or J/kg).

Intensive properties are those who do not depend on the amount of

matter (pressure, temperature, etc.). They are not additive.
Many properties can be expressed in both extensive and intensive
forms. For example, volume (V) versus molar volume (vm in m3/mol)
and specific volume (v^ in m3/kg)
3. Enthalpy (H)
Enthalpy (H)
First law: DU = Q + W
Change in U of a system that is free to expand or contract is not equal
to the energy supplied as heat (as some of that energy is used as work
produced to the surroundings)
The complication of having to take into account the work of expansion
of a system can be avoided by introducing Enthalpy.

For convenience we can define a term called enthalpy H (J) which is

the sum of internal energy U (J) and the PV work (P in N/m2 and V in
m3, so PV in J too).
H = U + PV

H is a state function, and we can write: DH = H2 – H1= DU + DPV

Enthalpy (H)
Applying the first law to a closed system
(Ek + Ep are negligible):

dU= dQ + dW = dQ –PdV (as dW = -PdV)

At constant V, dU = dQ – PdV (with PdV = 0)

dU = dQ (or DU = Q)

At constant P, dU = dQ – PdV
dU + d(PV) = dQ
dH= dQ (and often we will write: DH= Q)
(by combining the PV components with U)

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Caution: always double check sign convention used at the time
Enthalpy summary (so far)

Thus, the total energy of a gas in a container is its internal

energy plus the extra energy the gas had to exert by having
volume V and pressure P.
We call this total energy, the enthalpy H. For the system of
volume V and pressure P:
H = U + PV or in differential form dH = dU + d(PV)

Simple expressions to remember:

At constant V: DU = Q
At constant P: DH= Q
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Example
A perfect gas undergoes a reversible expansion from V1 to V2 at
constant temperature (isotherm).

We agree that the work is done by the gas, and that it will loose some of
its energy (Wrev <0)

- What is the change of Internal Energy (DU)?

- What is the change in Enthalpy (DH)?
Example
Calculate DU and DH for 1 kg of liquid water when it is vaporised at the
constant temperature of 100C and the constant pressure of 1.013 bar?
This will require 2,257 kJ of heat.

Imagine the liquid is in a cylinder with a frictionless piston (with constant

pressure of 1.013 bar, as heat is added, water evaporates, expanding its
volume to…???

DH = DU + DPV
At constant P: DH = Q
and DPV = PDV
Check specific volumes: V^liq = 0.001 and V^vap = 1.673 m3/kg
(Table B.5)
All the energy provided by Q is used to increase H:
Q = DH = 2,257 kJ and:
H = U + PV
DH = DU +DPV and = DU + PDV (when P is constant)

PDV = 1.013 bar x (1.673-0.001) m3 (need to convert bar in Pa)

169.4 kPa.m3 = 169.4 kJ
DU = 2,257 – 169 = 2,087 kJ
Which is closed to U^sat’steam (2,507) – V^sat’water (419)

Go and check it out in Table B.5 to be sure

 Heat of Vaporization for Water (is an Enthalpy)
What is heat of vaporization at 20oC?

Word of caution: values reported in textbook are from experiments and models, are empirical (not absolute–
theoretical), and therefore vary slightly from a reference to another
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Few important tips:
For most of our future exercises, it is a good idea to start
from the PV (or equivalent) diagram

p
Isothermal Process ( = 1)

p1

pi
T1
p2 ( > 1)
T2

V1 V2 V
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And to be able to name/identify all the potential changes/processes
available

･ 0 to 1= constant pressure heating,

･ 0 to 2= constant volume heating,
･ 0 to 3= reversible adiabatic compression,
･ 0 to 4= isothermal compression,
･ 0 to 5= constant pressure cooling,
･ 0 to 6= constant volume cooling,
･ 0 to 7= reversible adiabatic expansion,
･ 0 to 8= isothermal expansion. www.taftan.com/
thermodynamics/POLYTROP.HTM

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Strategy to Approach Thermo Problems

How do you attack problems for problems involving heat

work, or temperature change of a system/stream
during a process?

• Decide what is your system

• Write the PVT expression
• Write the first law energy expressions
• If there is expansion or compression, do these occur
adiabatically, isothermal, or reversibly? In any cases,
plot the change in a PV (or other) graph

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Homework
(next 6 slides)

Or online here (
https://vimeo.com/157684830)

Password: “ceic2000”

A rigid tank is divided into two equal parts by a partition.

One side has 5 kg of water at 200 kPa and 25oC and the
other side is vacuum.
The partition is removed and water expands into the
space. The water equilibrates with the surroundings to
return to 25oC.
• What is the volume of the tank?
• What is the final pressure?
• What is the heat transfer for this process?

Assumptions:
Tank is stationary (no kinetic or potential energy change)
The volume of the tank is fixed. Note because we had
vacuum in the upper portion of the tank originally, there is
no PV work. Pext = 0
There is no friction, shaft or electrical work etc.
We define the water and the space above it as the system.
This is closed system.

What is the original state of the water?

At 25oC , the saturation pressure is 0.0317 bar from steam
table (B.5). 200 kPa is way above this so we have
compressed liquid.
We can estimate the properties of compressed liquids with
saturated liquids at the same temperature.
Specific volume of water is approximately
V^sat. Liq. 25oC = 0.001 m3/kg
V1 = mass of liquid x specific volume
= 5 kg (0.001 m3/kg) = 0.005 m3

Vtotal of tank = 2 x 0.005 m3 = 0.01 m3 (“2 equal parts”)

At the final state,
Average specific volume = 0.01m3/5kg = 0.002 m3/kg
Is this a two phase system?
V^sat liquid 25oC = 0.001003 m3/kg This is between sat. liq. and sat.
vapor at this temperature
V^sat. Vapor 25oC = 43.340 m3/kg
Thus we have two phase system (which we would have
expected intuitively).
How much vapor do we have?
V^average = 0.002 m3/kg = x (V^sat.vapor 25oC) + (1 - x) V^sat. Liq 25oC
Where x is the mass fraction of vapor.

x = 2.3 x 10-5
Mass of vapor = 5kg (2.3 x 10-5) = 0.1150g
Volume of that vapor = Mass vapor x V^sat.vapor 25oC = 4.98L
Pressure = sat. Pressure at 25oC = 0.0317 bar
Heat transfer?

Net Energy transfer by work, heat and mass =system

Qin = U = m (U^2 – U^1) as W = 0!
U1 is approximately U^ of sat. liquid water at 25oC = 104.8 kJ/kg
We have determined quality to be x = 2.3 x 10-5
U^2 = (1 - x) U^sat liquid + (x) U^sat vapor
U^2 = U^sat. Liquid (1 - 2.3 x10-5) + U^sat. Vapor (2.3 x 10-5)
U^2 = 104.85 kJ/kg 2409.9 kJ/kg

Qin = 5 kg (104.85 - 104.8) kJ/kg = 0.25 kJ