Chapter 2 First Law and Other Concepts UTAS

Thermodynamics I
ENCH2102
Chapter 2
The First Law of Thermodynamics and

Other Concepts
Dr Rajan
Chapter 2
THERMODYNAMICS I
The First Law of Thermodynamics and

Other Concepts
2
University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬
Joule’s Experiments
Thermometer Joule’s findings:
Motor 1. For each fluid, a fixed amount of work
is required per unit mass for every
degree of temperature rise caused by
Water, or oil
stirring
or mercury
2. Original temperature of fluid can be
restored by the transfer of heat through
simple contact with a colder object
 Main conclusion: A quantitative relationship exists between

work and heat, or heat is a form of energy.
Thermodynamics3 I
Internal Energy
• The internal energy of a substance does
not include energy that it may possess as
a result of its macroscopic position or
movement.
• Rather it refers to energy of the molecules

internal to the substance.
4
Internal Energy
This type of energy is an intrinsic property
of the system.
It is stored within a substance due to intra-
and intermolecular activity.
- Continuous motion within molecules,
e.g rotation, internal vibration (kinetic)
- Sub-molecular forces holding atoms
together as molecules (potential)
5
Internal Energy
• It cannot be directly measured; there are no
internal-energy meters. As a result, absolute
values are unknown.
• However, this is not a disadvantage in

thermodynamic analysis, because only changes
in internal energy are required.
6
Internal Energy
• Although the absolute value of the internal energy of a system
cannot be measured, the changes in the internal energy can be
measured.
The internal energy U of a system will change if :

– Heat, Q passes into or out of the system
– Work, W is done on or by the system
– Mass enters or leaves the system
7
Forms of Energy
E = total energy of our system = internal + external
The internal energy, U = potential energy from intermolecular

forces
External energy: kinetic/potential energy -macroscopic
When external energy = 0, E = U
8
External Forms of Energy
Kinetic and Potential Energy
These types of energy reside with a

substance because of its macroscopic
position or motion with respect to a
reference.
9
THE FIRST LAW OF
THERMODYNAMICS
10
First Law in terms of
Energy of System and Surrounding
First law normally applies to the system and its

surrounding, its basic form is
(energy of the system) + (energy of the surrounding) = 0
11
First Law
Change of energy includes KE, PE, IE (U)
∆(KE) + ∆(PE) +∆(U) = Q + W
• Heat and work represent the energy in transit

across the boundary.
• Potential, Kinetic and Internal energy are

stored with matter.
12
Closed Systems
• If the boundary of a system does not
permit the transfer of matter between the
system and its surroundings, the system is
said to be closed, and its mass is
necessarily constant.
13
Energy Balance for Closed
Systems
Since no streams enter or leave a closed
system, no energy associated with matter is
transported across the boundary of the system.
All energy exchange between a closed system

and its surroundings then appears as heat and
work.
Total energy change of the surroundings

equals the net energy transferred to or from it
as heat and work.
14
Systems
The choice of signs used with Q and W depends on

which direction of transport is regarded as positive.
The sign conventions for heat transfer and work are
Heat transferred to the system is POSITIVE
Work done on the system is POSITIVE
15
Systems
16
Systems
Closed systems often undergo processes that
cause no change in the system other than in its
internal energy
17
Systems
• For differential changes:
• For a closed system of n moles
18
Internal Energy
• There exists a form of energy, known as internal
energy U, which is an intrinsic property of a
system, functionally related to the measurable
coordinates which characterize the system.
• For a closed system, not in motion, changes in

this property are given by the following
Equations:
19
State and Path Functions
– State function: is one whose change on going from
initial to final is independent of the route taken.
(thermodynamic function)
Ex: state functions are volume, V, pressure, P, and

temperature, T.
– Path function: if the change in a function is

dependent on the route taken. (Not thermodynamic
function)
Ex: Q and W

Extensive properties
Extensive properties depend on the
quantity of matter in the system.
Ex: Volume
21
Intensive properties
Intensive properties do not depend on the
quantity of matter present,
Ex: temperature and pressure.
22
Specific properties
Specific properties are extensive
properties per unit mass.
Ex: specific enthalpy, molar volume.
Specific properties are intensive because

they do not depend on the mass of the
system.
23
Steady State
• A system which is interacting with the
surroundings is said to have attained a
steady state condition when the properties
at a specified location in the system do not
vary with time.
24
EQUILIBRIUM
• Equilibrium is a word denoting a static
condition, the absence of change.
• In thermodynamics, it means not only the

absence of change but the absence of any
tendency toward change on a macroscopic
scale.
• Hence for a system at equilibrium all forces

are in exact balance.
25
Equilibrium state of a system
Equilibrium means balance of the driving

forces across all modes of interaction such
that there is no tendency for change in the
state of the system.
This means system has to be in

equilibrium with either surroundings or any
other system
26
Equilibrium state
• There are 3 main equilibrium state of process

engineering systems
i. Mechanical equilibrium
ii. Thermal equilibrium
iii. Diffusional equilibrium
27
Mechanical equilibrium
There is absence of any net driving force
for bulk mass transfer this means system
pressure P will be the same as that of
surrounding pressure Pext.
P = Pext
28
Thermal equilibrium
• No driving force for causing thermal interaction.
• The system temperature will be same as

surrounding temperature.
29
Diffusional equilibrium
• This means absence of net driving forces

for causing diffusion mass transfer.
30
The phase rule
For multi phase systems at equilibrium, the number
of independent variables that must be specified to
establish its intensive state is given by Gibb’s phase
rule.
F  2   N
π is the number of phases (a phase is a

homogeneous region of matter e.g. gas, mixture of
gases, liquid, crystalline solid etc),
N is the number of chemical species and
F is the degrees of freedom of the system.
31
Ex. 2.3
How many degrees of freedom has each of the
following systems?
(a)Liquid water in equilibrium with its vapor.

(b)Liquid water in equilibrium with a mixture of
water vapor and nitrogen.
(c)A liquid solution of alcohol in water in
equilibrium with its vapor.
32
Reversible and Irreversible
Processes
• If a system and surroundings can be
returned to its original state, then the
process is a reversible process.
• If the state of the surroundings has

changed then the process is an
irreversible process.
33
Reversible Processes
• A process is reversible when its direction
can be reversed at any point by an
infinitesimal change in external conditions.
Examples
i. Reversible Expansion of a Gas
ii. Reversible Chemical Reaction
34
Characteristics of Reversible
Process
i. frictionless
ii. never more than differentially removed from equilibrium
iii.Traverses a succession of equilibrium states
iv. driven by forces whose imbalance is differential in
magnitude
v. Can be reversed at any point by a differential change
in external conditions
vi. When reversed, retraces its forward path, and restores
the initial state of system and surroundings
35
Constant-V and Constant-P Processes
For closed system, the 1st law can be written as:
dU t  dQ  dW
d (nU )  dQ  dW (where Q & W are in J)
For mechanically reversible process:

dW   Pd (nV )
d (nU )  dQ  Pd (nV )
This is the general first-law equation for n moles of

homogeneous fluid in a closed system undergoing a
mechanically reversible process.
36
Constant Volume Process
If the process occurs at constant total volume, the

work is zero.
Reversible
Q = nΔU Constant-V
Non-flow process
37
Constant Pressure Process
First law:
d (nU )  dQ - Pd (nV ) dQ  d (nU )  Pd (nV )
dQ  d [n(U  PV )]
dQ  d (nH )
Q  nH
2-38 I
Thermodynamics
Constant Volume and Pressure Processes
Constant-P Isobaric
Q = nΔH Non-flow process
Reversible
reversible Isochoric
Q = nΔU Constant-V
Non-flow process
2-39 I
Thermodynamics
Enthalpy
Enthalpy H and is defined as
H = U + PV.
U is the internal energy of the system, P

the absolute pressure and V the volume of
the system.
40
Heat Capacity & Specific Heat
The heat capacity of a substance is the quantity
of heat to raise the temperature by one
degree.
The heat capacity of unit mass of the

substance is known as specific heat of the
substance.
Unit: [kJ/kg.oC] or [kJ/kmol.oC] or [kJ/kmol.K] or

[J/g.oC]
41
Heat Capacity at Constant Volume
42
Heat Capacity at Constant Pressure
CP – CV = R
43
Ex 2.5

Open System
• Industrial processes involve
system in which matter
crosses the system boundary
as streams that enter and
leave process equipment.
Such systems are said to be
open systems.
• Most equipment in chemical,

petroleum and related
processes are designed to
operate fluids that run
continuously
45
Mass Balance for Open Systems
Control volume: Region of space identified for analysis of open system (C.V.).
Control surface: a surface which separate control volume from its surrounding.
Consider the C.V. shown in the drawing,

where fluid with the C.V. is the
thermodynamic system for which mass and
energy balances are written
{Rate of mass change within the C.V.}= {Net rate of mass flow into C.V.}
dmCV
 Δ(m) fs  0
.
dt
Δ( m ) fs  m 3  m1  m 2
. . . .
Where : holds for difference between exit and inlet streams

2-46
fs: term applies for all flowing streams University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬
.
Since, m = Mass flow rate =  uA
dmCV
 Δ( uA) fs  0 Continuity equation
dt
Steady state flow process: condition within the control volume do not change
with time C.V. contains constant mass of fluid
Δ( ρuA) fs = 0
. .
• For single entrance and single exit system m: 1 = m2 = constant
or ρ1u1 A1 = ρ2u2 A2
. u1 A1 u2 A2 uA
or m= = = This form of Continuity equation
V1 V2 V finds frequent use
49
General Energy Balance for Open System
{Rate of change of energy within the C.V.} =
{Net energy transfer into the control volume} + Heat + Work
48
 What are the types of energy carried by the flowing streams?
IE, KE & PE = (U +u2/2 + gZ)
 Rate of energy transport by each stream

.
= (U + u 2 / 2 + Zg ) m
Taking into consideration the PV work of the streams, then
.
= (PV + U + u 2 / 2 + Zg) m
 Energy is also transported across the C.V. as heat and work
49
The energy balance equation can be written as:
Or
d (mU )CV . . .
+ Δ[( H + u / 2 + Zg ) m] fs = Q+ W
2
dt
For most applications, KE = PE ≈ 0
d (mU )CV . . .
+ Δ[m H ] fs = Q+ W
dt
50
Steady state flow Processes
Implies no change of mass (m = constat), &
No change of conditions within C.V. U = constant

. .
Δ[( H  u / 2  Zg ) m] fs  Q  W
2 .
(kJ/s)
For single entrance and exit to C.V., it can be shown that
Δu 2
ΔH + + g ΔZ = Q + W (kJ/kg)
2
51

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Thermodynamics I

The First Law of Thermodynamics and

The First Law of Thermodynamics and

 Main conclusion: A quantitative relationship exists between

• Rather it refers to energy of the molecules

• However, this is not a disadvantage in

The internal energy U of a system will change if :

The internal energy, U = potential energy from intermolecular

External energy: kinetic/potential energy -macroscopic

When external energy = 0, E = U

Kinetic and Potential Energy

These types of energy reside with a

First law normally applies to the system and its

(energy of the system) + (energy of the surrounding) = 0

∆(KE) + ∆(PE) +∆(U) = Q + W

• Heat and work represent the energy in transit

• Potential, Kinetic and Internal energy are

All energy exchange between a closed system

Total energy change of the surroundings

The choice of signs used with Q and W depends on

The sign conventions for heat transfer and work are

Heat transferred to the system is POSITIVE

Work done on the system is POSITIVE

• For a closed system of n moles

• For a closed system, not in motion, changes in

Ex: state functions are volume, V, pressure, P, and

– Path function: if the change in a function is

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

Ex: temperature and pressure.

Ex: specific enthalpy, molar volume.

Specific properties are intensive because

• In thermodynamics, it means not only the

• Hence for a system at equilibrium all forces

Equilibrium means balance of the driving

This means system has to be in

• There are 3 main equilibrium state of process

• No driving force for causing thermal interaction.

• The system temperature will be same as

• This means absence of net driving forces

π is the number of phases (a phase is a

N is the number of chemical species and

F is the degrees of freedom of the system.

(a)Liquid water in equilibrium with its vapor.

• If the state of the surroundings has

d (nU )  dQ  dW (where Q & W are in J)

For mechanically reversible process:

This is the general first-law equation for n moles of

If the process occurs at constant total volume, the

d (nU )  dQ - Pd (nV ) dQ  d (nU )  Pd (nV )

U is the internal energy of the system, P

The heat capacity of unit mass of the

Unit: [kJ/kg.oC] or [kJ/kmol.oC] or [kJ/kmol.K] or

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

• Most equipment in chemical,

Consider the C.V. shown in the drawing,

Where : holds for difference between exit and inlet streams

IE, KE & PE = (U +u2/2 + gZ)

 Rate of energy transport by each stream

Taking into consideration the PV work of the streams, then

 Energy is also transported across the C.V. as heat and work

For most applications, KE = PE ≈ 0

No change of conditions within C.V. U = constant

For single entrance and exit to C.V., it can be shown that