181CTDCHA2: Chemical Thermodynamics 2A

LEARNING UNIT 1B
The First Law and Other Basic
Concepts

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Definitions
 System: body of matter under consideration

 Surroundings: anything outside the system

 System and surroundings are separated by a

hypothetical/invisible and infinitesimally thin surface
called system boundary

 Universe is system and surroundings combined

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Illustration
■ System - everything
found within the central
container
■ Surroundings - made up
of the ice water bath, the
central container and
insulated container
■ Universe - the system
and surroundings
together (and stops at the
wall of the insulated
container)
Boundaries can be real or
imaginary, rigid or flexible
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Definitions (cont.)
 Open system: boundaries allow transport of matter and energy
between system and surroundings.

 Closed system: A closed system always contains the same matter.

There can be no transfer of mass across its boundary but energy
interchange is possible.

 Isolated system: special type of closed system that does not

interact in any way with its surroundings. No interchange of matter
and energy.
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Example of an Isolated System
A perfect thermal flask would be a good example,
unfortunately it does not exist

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Open, Closed and Isolated Systems
■ Consider the following system: Is this an open,
closed or isolated system?

(a) open, (b) closed, or (c) isolated

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Answer

In this system, no substances are leaving or

entering the system, heat is being
transferred to the molecules in the system
resulting in an increase in volume
i.e. CLOSED SYSTEM

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More Definitions
 Isothermal process - a process during which T remains constant
 Isobaric process - a process during which P remains constant
 Isochoric (or isometric) process - a process during which
specific volume (v) remains constant
Note: The prefix iso- is often used to designate a process for which a
particular property remains constant.

 Adiabatic process - a process where there is no heat transfer i.e.

Q remains constant
 Intensive properties – properties that do not depend on the
quantity of material involved e.g. T, P, 
 Extensive properties – properties that depend on the quantity of
material involved e.g. Vt, mt, Et

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Energy
Energy is a fundamental concept of thermodynamics and one of the
most significant aspects of engineering analysis.

In thermodynamic analysis, various forms of ‘energies’ that make up the

total energy of a system are considered in two groups: macroscopic and
microscopic
Macroscopic forms of Microscopic forms of energy
energy ■ Are concerned directly with the
■ Are concerned with the structure of matter
gross or overall behaviour ■ Are related to the molecular
structure of a system and the
■ Are those a system degree of the molecular activity,
possesses as a whole with and they are independent of
outside reference frames
respect to some outside
reference frame, such as ■ Sum of all microscopic forms of
energy is called the internal
kinetic and potential energy (U) of a system
energy

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First Law of Thermodynamics
This is an expression of the principle of conservation
of energy, which basically states that:

Although energy can be stored within systems in

various forms (e.g. work, heat and internal energy),
energy cannot be destroyed it is merely converted
from one form to another and transferred between
systems. Therefore total amount of all types of energy
always remains constant

[Click to view demonstration]

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Energy is added or removed from a system as work (W)
and/or heat and is contained in the system in the form of
internal energy (U)
BOUNDARY

HEAT (Q)
WORK (W) FLUID (SYSTEM)
INTERNAL
ENENRGY
SURROUNDINGS

Generally KE are PE terms are negligible (and are omitted

from the formula)
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Internal energy
 Energy possessed by molecules internal to
substance due to ceaseless motion. All molecules
possess kinetic energy of translation, rotation and
vibrations and potential energy resulting from
intermolecular forces
 Internal energy cannot be directly measured; there
are no internal-energy meters. As a result, absolute
values are unknown
 Internal energy does not include energy due to
macroscopic position or movement
 In thermodynamic analysis, only changes in internal
energy (U) are possible

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Internal energy (cont.)
 Heat added or work done on system:
 Increase U
 Heat removed or work done by system:
 Decrease U

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Heat and Work
 Heat – a form of energy that is transferred between two
systems (or a system and its surroundings) by virtue of
a temperature difference
 Work – energy transfer associated with a force acting
through a distance
 Addition of heat (Q) to a system increases molecular
activity, and thus causes an increase in internal energy
 Doing work (W) on a system increases molecular
activity , and thus causes an increase in internal energy
 If Q and W cross the boundary from surroundings
to system  sign is positive

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Heat and Work (cont.)

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Example 1
A gaseous system, enclosed in a cylinder, is compressed from
6.20L to 2.48L by a constant external pressure of 10.0kPa

a) Is work being done on the system or by the system?

b) Is the value of the work done going to be positive or
negative?
c) Is the internal energy of the system, U, increasing or
decreasing? Will U be negative or positive?
d) Calculate the work done by the surroundings on the system
[click here to reveal answer]
e) How do you know that work is being done on the system?

[click here to reveal answer]

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Example 2
■ Suppose the above process had been carried out in
two steps instead of one.
• First, external pressure was increased to 7.08 kPa
causing volume to decrease from 6.20 L to 3.50 L.
• Then the pressure was further increased to 10.0
kPa causing the volume to decrease to 2.48 L.

a) Calculate the work required [click here to reveal

solution]
b) How would you explain what has happened? [click
here to reveal solution]

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Additional Problems
■ Nitrogen gas is heated slowly, maintaining the
external pressure close to the internal pressure of 50
atm, until its volume has increased from 542 L to 974
L. Calculate the work done, in joules, on the Nitrogen
gas as it is heated.
[Answer: -2.19 x 106 J]

■ The gas mixture inside one of the cylinders of an

automobile engine expands against a constant
external pressure of 0.98 atm, from a volume of 150
mL to a volume of 800 mL. Calculate the work done,
in joules, on the gas mixture during this expansion.
[Answer: -65 J]
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Thermodynamic State and
State Functions
■ Thermodynamic state – set of values of properties
(state variables) of a thermodynamic system that
must be specified to reproduce the system

■ State functions/ parameters – measurable properties

required to describe the state of system e.g. T, P, V,
U

■ State functions do not depend on the ‘past history of

system’ or thermodynamic path followed

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 Changes in state functions indicate
differences between final and initial values

[Click for video ]

 Change in state function depends only on the

initial and final states and not on the path by
which the change occurs

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State Functions

Once a minimum number of variables have been

specified, values of all other properties of the
system become automatically fixed

For example, N2 gas at a temperature of 300K and

a pressure of 1 atm has a fixed volume or density or
a fixed molar internal energy

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State and Equilibrium
• When a system is not undergoing any change all its
properties (T, P, V) can be measured or calculated
throughout the entire system giving a set of properties that
completely describes the state of the system
• At a given state, all properties of a system have fixed
values and if the value of any one property changes, the
state will change to a different one

ICE WATER VAPOUR

m = 2 kg m = 2 kg m = 2 kg
T1 = 0oC T1 = 20oC T1 = 100oC
P1 = 1 atm P1 = 1 atm P1 = 1 atm

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State and Equilibrium (Cont.)
 Thermodynamics deals with equilibrium states

 Equilibrium implies a state of balance i.e. in an

equilibrium state there are no unbalanced potentials (or
driving forces) within the system

 A system in equilibrium experiences no changes when

it is isolated from its surroundings

 A system will not be in equilibrium unless all the

relevant equilibrium criteria are satisfied

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State and Equilibrium(Cont.)
These are the 4 types of equilibrium:
 Thermal equilibrium is when temperature is the same
throughout the entire system i.e. there is no temperature
differences, which is the driving force for heat flow
 Mechanical equilibrium is when pressure does not
change at any point of the system with time
 Phase equilibrium this involves two phases. It is when
the mass of each phase reaches an equilibrium
(constant) level and stays there
 Chemical equilibrium is when chemical composition
does not change with time i.e. no chemical reactions
occur

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Phase Rule
 The state of a pure homogeneous fluid is fixed
whenever two intensive thermodynamic properties
are set at definite values
 In contrast, when two phases are in equilibrium, the
state of the system is fixed when only a single
property is specified
 For example, a mixture of steam and liquid water in
equilibrium at 101.325 kPa (1 atm) can exist only at
373.15K (100°C)
 It is impossible to change the temperature without
also changing the pressure if vapour and liquid are to
continue to exist in equilibrium

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Phase Rule (cont.)

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Phase Rule (cont.)
 The intensive state of system at equilibrium is
established when its temperature (T), Pressure (P)
and the compositions of all phases are fixed

 These are phase-rule variables, but they are not all

independent

 F gives the minimum number of variables which

must be arbitrarily specified to fix all remaining
phase-rule variables
 When F = 0 the system is invariant
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Phase Rule (cont.)

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Example
Determine the degree of freedom for each of the
following systems

a) Liquid water in equilibrium with its vapour;

b) Liquid water in equilibrium with a mixture of water
vapour and nitrogen;
c) A liquid solution of alcohol in water in equilibrium with
its vapour.

Write all answers down and click here for answers when
done.

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Reversible Process
■ A process is reversible when the net driving force
is only differential (dT, dQ or dV) in size e.g. heat
is transferred reversibly when it flows from a finite
object at temperature T to another object at
temperature T – dT

■ The process can be reversed at any point by

differential (small) change in external conditions

■ When reversed, it retraces its forward path

returning to its initial state

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Reversible Process

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Example
A horizontal piston/cylinder arrangement is placed in a constant-
temperature bath.
The piston slides in the cylinder with negligible friction, and
an external force holds it in place against an initial pressure
of 14 bar.
The initial gas volume is 0.03 m3.
– The external force on the piston is reduced gradually, and
the gas expends isothermally as its volume doubles. If the
volume of the gas is related to its pressure so that the
product PV is constant, what is the work done by the gas
in moving the external force?
– How much work would be done if the external force were
suddenly reduced to half its value instead of being
gradually reduced?
Write all answers down and click here for answers when done .
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Constant Volume Process

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Constant Pressure Process

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Enthalpy

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Example

Write answer down and click here for solution when done

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Heat Capacity

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Heat Capacity (cont.)

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Heat Capacity (cont.)
 If the volume varies during the process but returns at
the end of the process to its initial value, the process
cannot ‘rightly’ be called one of constant volume,
even though:
V2 = V1 and V = 0
 However, changes in state functions or properties are
independent of path, and are the same for all
processes which result in the same change of state
 U, Cv and T are all state functions therefore U can
be calculated
 However, Q does depend on path followed and the
equation is used to get Q if and only if it is a
‘constant-volume process’
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Heat Capacity (cont.)
 Because U, Cv and T are state functions an actual
process may be replaced by any other process which
accomplishes the same change in state for
calculation of property changes

 For example, a process were the water temperature

changed from 10oC to 20oC after heating can be
replaced by a process were water temperature
changed from 50oC to 60oC

 The water is still in the same phase and Cv (almost

constant) and T are similar
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Heat Capacity (cont.)

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Example
Air at 1 bar and 298.15K is compressed to 5 bar and 298.15K by two
different mechanically reversible processes:
a) Cooling at constant pressure followed by heating at constant
volume;
b) Heating at constant volume followed by cooling at constant
pressure
Calculate Q and W required and ΔU and ΔH of the air for each
path
Heat capacities for air: Cv = 20.78 and Cp = 29.10 J mol-1 K-1
At 298.15K and 1 bar, molar volume of air: 0.02479 m3 mol-1
Assume (also for air) that PV/T is a constant, regardless of the
changes it undergoes

Click here for solutions when done

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Mass Balance for Open Systems

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Mass Balance for Open Systems

Conservation of mass principle for an ordinary bathtub

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Relationships between Flow
Measurement

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Mass Balance for Open Systems

When solving mass and energy balances for open

systems:
 Identify region of space for analysis, known as
control volume
 Control volume is separated from its surroundings
by a control surface
 Fluid within the control volume is the
thermodynamic system for which mass and energy
balances are written

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Mass Balance for Open Systems

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Mass Balance for Open Systems
(cont.)

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Example
A garden hose attached with a
nozzle is used to fill a 10-gal bucket.
The inner diameter of the hose is 2
cm, and it reduces to 0.8 cm at the
nozzle exit.
If it takes 50 s to fill the bucket with
water, determine
(a) the volume and mass flow rates
of water through the hose,
(b) the average velocity of water at
the nozzle exit

Take the density of water to be

1000 kg/m3 = 1 kg/L

Click here for solution when done

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Example
A feedwater heater operating at steady state has two inlets
and one exit.
At inlet 1, water vapour enters at P1 = 7 bar, T1 = 200oC
with a mass flowrate of 40 kg/s.
At inlet 2, liquid water enters at P2 = 7 bar, T2 = 40oC
through an area, A2 = 25 cm2.
Saturated liquid at 7 bar exits (3) with a volumetric
flowrate of 0.06 m3/s.
Take: v3=1.108x10-3 m3/kg and v2=1.0078x10-3 m3/kg
(from Steam tables)
Determine the mass flowrates at inlet 2 and at the exit, in
kg/s, and the velocity at inlet 2, in m/s

Click here for solution when done

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Energy Balance for Open Systems

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Energy Balance for Open Systems

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Energy Balance for Open Systems
(cont.)

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Examples of Steady-flow
Engineering Devices
• Many engineering devices operate essentially
under the same conditions for long periods of time
e.g. components of a steam power plant (turbines,
compressors, heat exchangers and pumps)
operate non-stop for months before the system is
shut down for maintenance

• These devices can be conveniently analysed as

steady-flow devices

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Example
An evacuated tank is filled with gas from a constant-
pressure line.
What is the relation between the enthalpy of the gas
in the entrance line and the internal energy of the gas
in the tank?
Neglect heat transfer between the gas and the tank

Click here for solution

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Example
An insulated, electrically heated tank for hot water contains
190 kg of liquid water at 60oC when a power outage
occurs.

• If water is withdrawn from the tank at a steady rate of

0.2 kg s-1, how long will it take for the temperature of
the water in the tank to drop from 60 to 35oC?

Assume that cold water enters the tank at 10oC, and that
heat losses from the tank are negligible.
For water, let Cv=Cp = C, independent of T and P

Click here for solution

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Energy Balance for Steady-
state Flow Processes

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Example
Air at 1 bar and 25oC enters a compressor at low
velocity, discharges at 3 bar, and enters a nozzle in
which it expands to a final velocity of 600 ms-1 at the
initial conditions of pressure and temperature.

• If the work of compression is 240 kJ per kilogram

of air, how much heat must be removed during
compression?
Click here for solution

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Example
Air enters a nozzle steadily at 2.21 kg/m3 and 40 m/s
and leaves at 0.762 kg/m3 and 180 m/s. If the inlet
area of the nozzle is 90 cm2, determine:
(a) the mass flow rate through the nozzle, and
(b) the exit area of the nozzle.

The density of air is given to be 2.21 kg/m3 at the inlet

and 0.762 kg/m3 at the exit.

Click here for solution

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Example
A garden hose attached with a nozzle is used to fill a
20-gal bucket.
The inner diameter of the hose is 1 in and it reduces to
0.5 in at the nozzle exit.
If the average velocity in the hose is 8 ft/s, determine:
(a) the volume and mass flow rates of water through the
hose,
(b) how long it will take to fill the bucket with water, and
(c) the average velocity of water at the nozzle exit.

Click here for solution

Take the density of water to be 62.4 lbm/ft3.

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Example
Steam is leaving a 4 L pressure cooker whose operating pressure is 150
kPa. It is observed that the amount of liquid in the cooker has decreased
by 0.6 L in 40 min after the steady operating conditions are established,
and the cross-sectional area of the exit opening is 8 mm2. Determine:
(a) the mass flow rate of the steam and the exit velocity,
(b) the total and flow energies of the steam per unit mass, and
(c) the rate at which energy leaves the cooker by steam

Properties of saturated liquid water and water vapour at 150 kPa are:
vf = 0.001053 m3/kg,
vg = 1.1594 m3/kg,
Click here for solution
Ug = 2519.2 kJ/kg, and
Hg = 2693.1 kJ/kg (from Steam tables)

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Homework - read Chapter 2 in the textbook:
Smith, J.M., Van Ness, H.C., Abbott , M.M. (2005),
Introduction to Chemical Engineering
Thermodynamics. 7th Edition, McGraw-Hil

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 Tips
Need to work in pairs and not stay
isolated from the other students (need
to develop working relationships and
get to know each other) [Click here if
you would like to see quotes about
teamwork)

Important to use the tutorial sessions

productively i.e. prepare for the sessions
and discuss issues/ challenges with the
tutor/s

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At the end of this course you
should have attained these
outcomes

■ Applying Thermodynamic principles to diagnose

and solve engineering problems.

■ Demonstrate engineering knowledge and skills

in the Thermodynamics field.

■ Engage in Thermodynamics work individually

and as part of a team.

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