Chemical Engineering

Thermodynamics I

CHE345

Engr. Dr. Ayoola Ayodeji 1

General Introduction: First
and Second Laws of
Thermodynamics
2
 INTRODUCTION
System: portion/object to be studied
Surroundings: everything external to the system
Boundary: what separates a system from its surroundings.
Open System (control volume): a system that allows mass and energy
interaction between the system and its surroundings.
 INTRODUCTION
Closed System: a system with no mass interaction between
the system and the surroundings
Properties:
What describe a system.
Macroscopic characteristics of
a system and can be assigned
numerical values

State:
Condition/position of a system
due to change in properties
 INTRODUCTION
Process: a series of changes experience by a system
from one state to another.
The path of successive states through which a system
passes when change from one state to another.
Reversible Process: a system undergoes reversible
process when it is restored to its initial state following
same manner.
 INTRODUCTION
Cyclic process: a system undergoes
thermodynamic cyclic process when it is restored
to its initial state.

Equilibrium: state of balance, a system in

equilibrium experiences no changes when it is
isolated from its surroundings.
It is a condition of constant property.
 Example 1
As shown in the figure, water which
circulates between a storage tank and
a solar collector is used for domestic
purposes. Identify locations on the
system boundary where the system
interacts with the surroundings and
describe events that occur within the
system, if the system is
[a] solar collector
[b] solar collector, storage tank and
connecting pipes.
Solution
[a] The system (solar collector) is
an open system.
Warm water enters the system at
the base through the pump.
The water is heated up as a result
of heat radiation through the
surface of the system.
Hot water leaves the system at the
top.
Pressure exerted on the system
through the pump makes upflow
of water possible.
 Solution
[b] The system consisting of the solar
collector, the tank and pipes is an open
system.
Cold water enters the tank at the base and
get warm on mixing with hot water inside
the tank.
There is interaction between the
surroundings, surface of the tank, water
inside the tank.
Warm water entering solar collector
interacts with the surroundings at the
surface of the collector and becomes hot
water.
Hot water in the tank leaves the tank the
moment the water level rises to the top.
 Exercise

As illustrated in the figure, water

circulates through a piping
system, servicing various
household needs.
Considering the water heater as
a system, identify locations on
the system boundary where the
system interacts with its
surroundings and describe
significant occurrence within the
system. Repeat for the
dishwasher and for the shower.
 First law of Thermodynamics

Although energy assumes many forms, the total quantity

of energy is constant, and when disappears in one form it
appears simultaneously in other forms.

………that is during an interaction between a system and its surroundings, energy can
change from one form to another but the total amount of energy remains constant,
that is, energy can neither be created nor destroyed.
 First law of Thermodynamics
The law implies that
• There are different forms of energy
• There is conservation of energy
• Total energy between a system and its surroundings is constant (no change in
total energy between a system and its surroundings)
The last expression can be written as

Δ(Energy of the System) + Δ(Energy of the Surroundings) = 0

2.1
where Δ ≡ change
 WORK, W
• Work is a form of energy transferred between the system and
surroundings.
• It can only be transferred, but not stored (transient energy)
• Work can done by a system on its surroundings and work can be done
by surroundings on a system.
+ve sign is assigned when work is done on the system
-ve sign is assigned when work is done by the system
• W is not a point function, but path function (i.e. its magnitude depends
on the process path).
 WORK, W
2
• For finite process, W = ‫׬‬1 F dS
• For infinite process, dW = F dS
• In Engineering thermodynamics, the predominant type of work
involves expansion and contraction of a fluid
2
W= ‫׬‬1 p dv
 WORK, W
In a piston-cylinder arrangement, and the piston is withdrawn in such a
way that the pressure remains constant. The initial pressure and volume
are 10 kPa and 0.1m³, respectively. Calculate the work done by the gas on
the piston, if expands to 0.3m³ .
Solution
2
W= ‫׬‬1 p dv
2
W= p ‫׬‬1 dv
W = p [v2 - v1 ] = 10 (0.3 – 0.1)
= 2 kJ
Heat, Q
• Heat is a form of energy which, when transferred to or from
a system makes it hotter or colder, respectively.
• Heat and work are energy in transit, between a system and
its surroundings.
• Energy interaction is heat only if it takes place because of
temperature difference.
• There cannot be any heat transfer between two systems
that are at the same temperature.
Heat is recognized only as it crosses the boundary of a
system
Internal Energy, U
• Internal Energy, U, is the macroscopic
measure of molecular and atomic energies of
a system.
• It is a state function.
• It can not be measured directly, but it can be
calculated in terms of measurable properties
such as P, V, T.
• Change in internal Energy, ∆U, is expressed
2
as ∆U = ‫׬‬1 CV dT
 Enthalpy, H
•It is a state function. That is, it depends only on the state of the system, but not
on how the system reached the state.
•It is particularly useful in processes occurring at constant pressure, such as
chemical reactions in open containers.
• Enthalpy is defined using combination of properties.
The enthalpy, H, is defined as:
H = U + PV and *
∆H = ∆U + ∆(PV) **
where U is Internal Energy, P is Pressure and V is volume.
• For a constant P and V process,
∆H = ∆U ***
also
Q = n∆H = n∫CpdT ****
 Energy Balance For A Closed System
• For a closed system, no form of energy is transported
between the system & surroundings.
• The only forms of energy that may be transferred are Heat
(Q) and Work (W).
• The second term of Equation 2.1 can be written as
Δ(Energy of the Surroundings) = ±Q ±W 2.2
• Q and W denote Heat and Work of the system.
• The sign used depends on the nature of the energy and
convention adopt, +ve sign is taken as energy to the system
 Energy Balance For A Closed System
Hence,
Qsurr. = -Q, Wsurr. = -W 2.3
Equation 2.1 becomes
Δ(Energy of the System) + [ – Q – W ] = 0
Δ(Energy of the System) = Q + W
i.e. Change in Total Energy of a closed system equals net
energy transferred to it in form of heat and Work.

Total Energy of a𝐭 closed system is represented as Total

Internal Energy (𝐔 ) of the system.
so
Δ𝐔 𝐭 = Q + W 2.4
For differential change, 𝒅𝑼𝒕 = dQ + dW
 Example 2.3
One mole of gas in a closed system undergoes a
four-step thermodynamic cycle. Use the data
given in the following table to determine
numerical values for the missing quantities.
Step ΔU /J Q /J W /J
12 -200 - -6000
23 - -3800 -
34 - -800 300
41 4700 - -
12341 - - -1400
Solution To Example 2.3
A Thermodynamic Cycle

1
2

4
3
Solution To Example 2.3
t
For a closed system, ΔU = Q + W
Step 1 – 2: ΔU = Q + W
12 12 12

-200 = Q + (-6000)
12

⟹ Q = 5,800 J
12

Step 3 – 4: ΔU = Q + W
34 34 34

ΔU = -800 + 300
34

ΔU = -500 J
34
Solution To Example 2.3
For a closed system, ΔU t = 0
ΔU1234 = 0 = Q1234 + W12343
⟹ Q1234 = -W1234 = 1400 J

Q1234 = Q12 + Q23 + Q34 + Q41

Q41 = Q1234 - Q12 - Q23 - Q34
= 1400 – 5800 + 3800 + 800
Q41 = 200 J
Solution To Example 2.3
Step 4 – 1: ΔU41 = Q41 + W41
4700 = 200 + W41
⟹ W41 = 4500 J

ΔU1234 = 0 = ΔU12 + ΔU23 + ΔU34 + ΔU41

0 = -200 + ΔU23 - 500 + 4700
⟹ ΔU23 = -4000 J
Solution To Example 2.3
Step 2 – 3: ΔU23 = Q23 + W23
-4000 = -3800 + W23
⟹ W23 = -200 J
Hence the table becomes
Step ΔU /J Q /J W /J
12 -200 5,800 -6000
23 -4000 -3800 -200
34 -500 -800 300
41 4700 200 4500
12341 0 1400 -1400
Introduction
• Can one form of energy be completely converted to
another form? In practice, when energy is
transferred from one form to another, there is
often a degradation of the supplied energy into a
less useful form.

• Second Law of Thermodynamics addresses some

of these difficulties
 Importance of the Second Law
Some of the importance of the second law are:
1. Prediction of process direction.
2. Establishment of equilibrium conditions.
3. Determination of the best theoretical performance of
cycles, engines and other devices.
4. Quantitative evaluation of factors that preclude the
attainment of the best theoretical performance level.
5. Determination of properties such as U and H in terms
of more readily experimentally determined properties.
 Commonly Used Terms
• Heat (thermal) reservoir is a sufficiently large system in
stable equilibrium to which and from which finite
amounts of heat can be transferred without any change
in its temperature.
• A high temperature heat reservoir from which heat is
transferred is sometimes called a
heat source (eg. furnace). A low
temperature heat reservoir to
which heat is transferred is
sometimes called a heat sink (eg.
atmosphere).
Commonly Used Terms
• Work reservoir is a sufficiently large system in stable
equilibrium to which and from which finite amounts
of work can be transferred adiabatically without any
change in its pressure.

• Thermodynamic cycle: A system has completed a

thermodynamic cycle when the system undergoes a
series of processes and then returns to its original
state, so that the properties of the system at the end
of the cycle are the same as at its beginning.
 Commonly Used Terms
• A reversible process is one in which both the system and
its environment can be returned to exactly the states they
were in before the process occurred.

• Heat Engine: A device or machine that produce work from

heat in a cyclic process. E.g. Steam power plant in which
the working fluid (H2O) periodically returns to its original
state.
A thermodynamic system operating in a thermodynamic
cycle to which net heat is transferred and from which net
work is delivered.
Commonly Used Terms

• Working substance of the engine is the material

within the engine that actually does the work.
Examples include steam in steam power plant and
the gasoline-air mixture in an automobile engine.
 Heat Engine
• Work can be easily converted completely to other forms of energy
• Converting other forms of energy to work is not that easy
• Work can be converted to heat directly and completely
• Heat can be converted to work directly, but not completely
• Converting heat to work requires the use of certain devices such as heat engine
• Heat engines come in many forms, pure heat engines (steam power plants) and
semi heat engines
(gas turbines)
• Each heat engine operates by using
a working substance (fluid).
 Heat Engines
• They receive heat from a high-temperature source (eg. Furnace).
• They convert part of this heat to work
(mostly through rotating shaft).
• They reject the waste heat to low-
temperature sink (eg. Atmosphere, River).
• They operate on a cycle
• Purposely built to convert heat
to work.
 Heat Engine
Qin = amount of heat supplies to steam
in boiler from high temperature source
(furnace)
Qout = amount of heat rejected from
steam in condenser to a low-
temperature sink
Wout = amount of work delivered by
steam as it expands in turbine
Win = amount of work required to
compress water to boiler pressure
Wnet = Wout - Win (kJ)
Wnet = Qin - Qout (kJ)
Heat Engine Efficiency
Class Work
1. Which of the following heat engine conditions
is preferred in each case:
a) absorbed heat of 300 J and discarded 50 J of heat
b) absorbed heat of 350 J and 300 J of work done
c) 400 J of work done and 100 J of heat discarded.
 Refrigerators and Heat Pumps
• Heat moves in nature from high temperatures to
lower temperatures, no devices required.
• The reverse process, heat from low temperatures to
high temperature, requires
special devices called refrigerators
or heat pumps.
• Working fluid used in refrigeration
cycle is called a refrigerant.
The objective of refrigerator is to
remove heat from the refrigerated space
 Refrigerators and Heat Pumps
• The refrigerant enters the compressor as vapour and compressed to
condenser pressure
• It condenses as it flow through the coils of the condenser by rejecting
heat to the surrounding medium
• Its pressure and temperature drop drastically
as it expands in capillary tube.
• It evaporates in evaporator by absorbing
heat from the refrigerated space.
 Refrigerators and Heat Pumps
• In household refrigerator, the freezer compartment (where heat is
absorbed by the refrigerant) is the evaporator.
• Coils behind the refrigerator (where heat is dissipated to surroundings)
is the condenser.

In a refrigerator, the interior

of the unit is the cold reservour,
while the warmer exterior
is the hot reservour.
 Heat Engine vs Heat Pump

In the refrigeration process, work W is used to remove

heat QC from the cold reservoir and deposit heat QH
into the hot reservoir.
 Coefficient of Performance (COP)
The index of performance of a refrigerator or heat pump is
expressed in terms of the coefficient of performance, COP, the
ratio of desired result to input.
Coefficient of Performance,
Desired Output QL
𝑪𝑶𝑷𝑹 = =
Required Input Wnet,in
QL 1
= = Q𝐻
Q𝐻 − QL −1
QL
Coefficient of Performance of a
refrigerator can be greater than 1.
While the efficiency of a heat engine
must always be less than 1
 Coefficient of Performance (COP)
Efficiency of a Heat Pump,
Desired Output QH
𝑪𝑶𝑷𝑯𝑷 = =
Required Input Wnet,in
Q𝐻
=
Q𝐻 − QL
1
= Q𝐿
1−
QH

The objective of a Heat Pump is to maintain

a heated space at a high temperature, by
absorbing heat from a low
temperature source.
 Exercises
1. A steam power plant with a power output of 150 MW
consumes coal at a rate of 60 tons/h. If the heating value
of the coal is 30,000 kJ/kg, determine the overall
efficiency of this plant.
2. A heat pump is to provide 2000 kJ/h to a house
maintained at 20°C. If it is −20°C outside, what is
the minimum power requirement?
3. A heat pump is to maintain a house at 20°C when the
outside air is at −25°C. It is determined that 1800 kJ is
required each minute to accomplish this. Calculate the
minimum power required.
4. Study the given figure and
determine:
a) The power input, in
kW.
b) The lowest theoretical
temperature inside the
refrigerator, in K.