Chemical Engineering Process

Analysis 1
(CHE 310)
Concepts and Units of Energy
Lecture 1

1
 Concepts and Units of Energy
Preamble
• The concept of energy conservation as expressed by an energy
balance equation is central to chemical engineering calculations.
• Similar to mass balances studied previously, a balance on energy is
crucial to solving many problems.
• In process design, energy balances are made to determine the energy
requirements of the process: the heating, cooling and power
required.
• In plant operation, an energy balance (energy audit) on the plant will
show the pattern of energy usage, and suggest areas for conservation
and savings.
2
System
• A “system” is a region chosen for study enclosed by a boundary. The
system has a definite boundary, called the system boundary, that is
chosen and specified at the commencement of the analysis.
• The boundary is the surface that separates system from surroundings
• Once a system is defined, through the choice of a system boundary,
everything external to it is called the surroundings.
• All energy and material that are transferred out of the system enter
the surroundings, and vice versa.
• In the general case there are very few restrictions on what a system
is; a system can have a nonzero velocity, a nonzero acceleration, and a
system can even change in size with time.
3
Types of system
• An isolated system is a system that does not exchange heat, work, or
material with the surroundings.
• If heat and work are exchanged across a system’s boundary, but
material is not, it is a closed system.
• An open system can exchange heat, work, and material with the
surroundings.

4
Review of Terminologies
• Properties: observable characteristics of the system.
• Steady state: accumulation is zero
• Unsteady state: there is accumulation
• Equilibrium: thermal, mechanical, phase and chemical properties
of the system are invariant
• Phase: physically distinct component (solid, liquid, vapour).
Energy is associated with phase change.

5
Energy Terminologies
• Adiabatic system
A system that does not exchange heat with the surroundings during a
process (perfectly insulated)
• Isothermal system
A system in which temperature does not change during a process
• Isobaric system
A system in which pressure does not change during a process
• Isochoric system
A system in which volume does not change during a process

6
State of a System
• Once a system is defined, a certain number of variables will specify its
state fully.
• For example, one may need to provide the temperature, pressure,
composition, total amount of material, velocity, and position in order
to specify a system’s “state.”
• The exact information that is needed to specify the state of a system
depends on the type of system and the analysis to be performed.

7
• State variables
• A variable that depends only on the state of the system and not on
how the process occurred
• State function or point function
• Example is internal energy
• Path function
• A variable that depends on how the process takes place
• Path function
• Example is heat and work

8
Types of properties
• Intensive property
• Physical property of a system that does not depend on the size of
the system
• Example include, temperature, density, viscosity
• Extensive property
• Property of a system that is directly proportional to the size of the
system
• Example include mass, volume
• Specific properties
• Intensive property that is obtained by dividing an extensive
property by the total amount of the process material
• Example include, specific volume, specific growth rate
9
State Functions and State Properties
• The state of a system can be changed, for example by increasing its
temperature or changing its composition.
• Properties of the system whose change depends only on the initial (before) and
final states of the system, but not on path (the manner used to realize the
change from the initial to the final) state, are referred to as state properties or
state functions.
• Mathematically, the change in a state function or state property X, between
some final (state 2) and initial (state 1) situations, can be expressed as
∆𝑋 = 𝑋𝑓𝑖𝑛𝑎𝑙 − 𝑋𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ≡ 𝑋𝑠𝑡𝑎𝑡𝑒 2 − 𝑋𝑠𝑡𝑎𝑡𝑒 1 (1)
• In equation 1, 𝑋𝑓𝑖𝑛𝑎𝑙 only depends on the final state of the system, and 𝑋𝑖𝑛𝑖𝑡𝑖𝑎𝑙
only on the initial state of the system.
• Equation 1 does not require any information whatsoever as to how the system
got from the initial to the final state, since X does not depend on the details of
the path followed.
10
Forms of Energy
i. Potential energy, 𝑷𝑬
• It is the energy due to position. It is the form of energy stored by the
system because of its position in a potential field such as a gravitational
field. In a gravitation field, it may be calculated from the relation:
Potential energy = 𝑚𝑔𝑧
• Where 𝑚 = mass of the system (in kg), 𝑧 = height above some arbitrary
datum (in meters) and 𝑔 = gravitational acceleration with a value of
approximately 9.81 𝑚Τ𝑠 2 .
Worked Example
Crude oil is pumped at a rate of 15𝑘𝑔/𝑠 from a point 220𝑚 below the
ground to 20𝑚 above ground level. Calculate the rate of increase in
potential energy.
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SOLUTION

𝑃𝐸 = 𝑚𝑔∆𝑧
ሶ
𝑘𝑔 𝑚
= 15 × 9.81 2 × 20 − −220 𝑚
𝑠 𝑠
= 35.32 𝑘𝐽/𝑠

12
ii. Kinetic energy, 𝑲𝑬
• It is the energy due to motion. It is the form of energy stored by the
system as indicated by its velocity relative to the surroundings
1
𝐾𝑖𝑛𝑒𝑡𝑖𝑐 𝑒𝑛𝑒𝑟𝑔𝑦 = 𝑚𝑣 2
2
• where 𝑣 = velocity of the system, measured in 𝑚Τ𝑠.

Worked Example
Water flows into a process through a 2 𝑐𝑚 inner diameter pipe at
2.00 𝑚3 Τℎ . Calculate the kinetic energy for the system in 𝐽/𝑠.

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SOLUTION
1
𝐾𝐸 = 𝑚𝑣 2
2
𝑚 =? , 𝑣 =?
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒
𝐹𝑙𝑜𝑤𝑟𝑎𝑡𝑒, 𝐹 =
𝑑𝑒𝑛𝑠𝑖𝑡𝑦
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒, 𝑚ሶ = 𝐹𝜌
𝜌 = 1000𝑘𝑔/𝑚3 , 𝐹 = 2.00 𝑚3 Τℎ
𝑚ሶ = 2000𝑘𝑔/ℎ
𝑘𝑔 1ℎ
𝑚ሶ = 2000 × ×
ℎ 3600𝑠
𝑚ሶ = 0.556𝑘𝑔/𝑠
𝑣 =?

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 𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒, 𝐹
Linear velocity, 𝑣 =
𝑐𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎, 𝐴
The cross sectional area of the pipe is 𝜋𝑟 2
2 𝑚3 Τℎ 1ℎ
𝑣= 2 2
×
𝜋(0.01) 𝑚 3600𝑠
𝑣 = 1.77 𝑚/𝑠
1
𝐾𝐸 = × 0.556 × (1.77)2
2
= 0.870𝐽/𝑠

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iii. Internal energy, 𝑼
• This is the energy associated with molecular motion. Internal energy
is a macroscopic measure of the molecular, atomic, and subatomic
energies. It is a point or state variable. There is no direct way of
measuring internal energy but it is known to depend on temperature
and volume. The temperature 𝑇 of a material is a measure of its
internal energy 𝑈.
• For single phase, single component
𝑈 = 𝑓(𝑇, 𝑉)
• Taking the total derivative of 𝑈,
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
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• Change in internal energy when the process is isothermal is almost
zero, therefore the second term can be neglected.
𝜕𝑈 𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉 ≈ 𝑑𝑇
𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑈
• By definition, is the “heat capacity” at constant volume.
𝜕𝑇 𝑉
• Changes in internal energy (∆𝑈) can now be computed as
𝑈2 𝑇2
∆𝑈 = 𝑈2 − 𝑈1 = න 𝑑𝑈 = න 𝐶𝑣 𝑑𝑇
𝑈1 𝑇1

17
• Only the difference in internal energy can be calculated, not absolute
values.
• Internal energy relative to reference point can be calculated.
• When there is phase change, the integral equation is not valid;
because there is internal energy associated with phase change, which
has to be accounted for separately and it cannot be brought into this
integration.

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Example
What is the change in internal energy for a constant volume system if
1𝑘𝑔 of water at 100 𝑘𝑃𝑎 was heated from 0℃ to 100℃ and then
cooled back to 0℃ and 100 𝑘𝑃𝑎?

19
Worked Example
What is the change in internal energy when 10 𝑘𝑚𝑜𝑙 of air is cooled
from 60℃ to 30℃ in a constant volume process? 𝐶𝑉 = 2.1 ×
104 𝐽/(𝑘𝑚𝑜𝑙)(℃)

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SOLUTION
𝑇2
∆𝑈 = න 𝐶𝑣 𝑑𝑇
𝑇1
30
= න (2.1 × 104 )𝑑𝑇
60
෡ = 2.1 × 104 (30 − 60)
∆𝑈
For 10 kmoles of air, ∆𝑈 = −6.3 × 106 𝐽

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• Summarily, internal energy
• Depends on the chemical composition, state of aggregation and
temperature of the system
• Total internal energy of a system containing ′𝑁′ components
𝑁
෡𝑖
𝑈𝑡𝑜𝑡 = ෍ 𝑚𝑖 𝑈
𝑖=1
• Is independent of pressure for ideal gases and nearly independent of
pressure for solids and liquids
• i.e. For ideal gases, 𝑈 is a function of 𝑇 only.
• If temperature and phase do not change, no reaction occurs and
pressure change is less than a few 𝑎𝑡𝑚, then ∆𝑈 = 0

22
iv. Enthalpy, 𝑯
• In energy balances, the terms (U + PV) appears very often, hence, it
was defined accordingly and referred to as enthalpy. It is the measure
of the total energy of a thermodynamic system. Enthalpy is a state
function and an extensive quantity.
𝐻 = 𝑈 + 𝑃𝑉
• For a single phase, single component, 𝑓 𝑇, 𝑃
• Taking the total derivative of H,
𝜕𝐻 𝜕𝐻
𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇

23
• For small pressure differences, the second-term is small compared to
the first term. At lower pressures, the term can be removed for all
processes.
• Hence,

𝜕𝐻 𝜕𝐻 𝜕𝐻
𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃 ≈ 𝑑𝑇
𝜕𝑇 𝑃
𝜕𝑃 𝑇
𝜕𝑇 𝑃
𝜕𝐻
• By definition, is the “heat capacity” at constant pressure.
𝜕𝑇 𝑃
• Changes in enthalpy (∆𝐻) can now be computed as:
𝐻2 𝑇2
∆𝐻 = 𝐻2 − 𝐻1 = න 𝑑𝐻 = න 𝐶𝑃 𝑑𝑇
𝐻1 𝑇1
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• Integral equation is not valid if there is phase change
𝜕𝐻
• At higher pressures, is not negligible
𝜕𝑃 𝑇
𝜕𝐻
• is evaluated from experimental values.
𝜕𝑃 𝑇
• For ideal gases, enthalpy is a function of 𝑇 only. As long as there is no
𝑇2
phase change ∆𝐻 = ‫ 𝑇𝑑 𝑃𝐶 𝑇׬‬remains valid.
1
• Only difference can be calculated, not absolute values
• Enthalpy relative to a reference point can be calculated
• Total enthalpy of a system containing more than one component is
given as:
𝑁
෡𝑖
𝐻𝑡𝑜𝑡 = ෍ 𝑚𝑖 𝐻
𝑖=1
25
Worked Example
• The air you breathe is immediately warmed up from ambient
temperature to 37℃ before entering into your lungs. Calculate the
specific enthalpy change when the temperature of air is raised from
20℃ to 37℃. Assume that air is bone-dry. (Given: 𝐶𝑃 of air= 28.94 +
0.4147 × 10−2 𝑇 + 0.3191 × 10−5 𝑇 2 − 1.965 × 10−9 𝑇 3 𝐽/𝑚𝑜𝑙. ℃

26
SOLUTION
𝑇2
෡ = න 𝐶𝑃 𝑑𝑇
∆𝐻
𝑇1
37
= න (28.94 + 0.4147 × 10−2 𝑇 + 0.3191 × 10−5 𝑇 2 − 1.965 × 10−9 𝑇 3 )𝑑𝑇
20
෡ = 492.45𝐽/𝑚𝑜𝑙
∆𝐻

27
v. Heat
• When there is a difference in temperature between two points, heat
is transferred (flows) from high temperature to the low temperature.
• Heat is the energy transfer due to temperature difference.
• Heat taken in by a system from its surroundings is conventionally
taken as positive and that given out as negative.
• Heat cannot be stored by the system.
• Mathematically, 𝑄 = 𝑈𝐴∆𝑇
• Where 𝑈 = heat transfer coefficient determined empirically
𝐴 = area for heat transfer
∆𝑇 = temperature difference
28
vi. Work
• Energy transfer due to anything other than temperature difference,
such as force, torque or voltage.
• Work cannot be stored by the system.
• Work done on a system by its surroundings may be conventionally
taken as positive.
• Then, work done by the system on the surroundings as negative.
• This convention is arbitrary and some texts follow the opposite

29
• When work is done when a force acts through a distance.
𝑠𝑡𝑎𝑡𝑒 2
𝑊=න 𝐹𝑑𝑥
𝑠𝑡𝑎𝑡𝑒 1
• where 𝐹 =force measured in Newton, 𝑥 =distance (in meters).
𝑉𝑓
• When the work arises from a change in pressure or volume: 𝑊 = ‫𝑉𝑑𝑃 𝑉׬‬
𝑖
• where 𝑃 = pressure, Pa (N/𝑚2 ), 𝑉 = volume per unit mass, 𝑚3 .
• To integrate this function, the relationship between pressure and volume
must be known.
• In process design an estimate of the work done in compressing or
expanding a gas is often required.
• A rough estimate can be made by assuming either reversible adiabatic
(isentropic) or isothermal expansion, depending on the nature of the
process.
30
• For isothermal expansion (expansion at constant temperature):
𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• For reversible adiabatic expansion (no heat exchange with the
surroundings):
𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• where 𝛾 = ratio of the specific heats = 𝐶𝑝 Τ𝐶𝑣 .
• 𝐶𝑝 = 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒,
• 𝐶𝑣 = 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒

31
Types of work
• Mechanical work: occurs when mechanical force moves the
boundary of a system
• Electrical work: occurs when an electrical current passes through an
electrical resistance in the circuit
• Shaft work: occurs by a force acting on a shaft to turn it against a
mechanical resistance
• Flow work: flow work is performed on the system when fluid is
pushed into the system by the surroundings. For instance, when a
fluid enters a pipe, some work is done on the system to force the fluid
into the pipe. Similarly, when fluid exits the pipe, the system does
some work on the surroundings to push the exiting fluid into the
surroundings
32
Worked Example (mechanical work)
An ideal gas at 300K and 200kPa is enclosed in a cylinder by a
frictionless piston, and the gas slowly forces the piston so that the
volume of the gas expands from 0.1 to 0.2𝑚3 . Calculate the work done
by the gas on the piston if
a. isobaric path is used.
b. isothermal path is used

33
SOLUTION
For isobaric system, P is constant
𝑉𝑓
𝑊 = න 𝑃𝑑𝑉
𝑉𝑖

𝑉𝑓
= 𝑃 න 𝑑𝑉
𝑉𝑖

𝑃(𝑉𝑓 − 𝑉𝑖 )

200 × 103 (0.2 − 0.1)

20 × 103 𝐽

20𝑘𝐽 34
For isothermal process, temperature is constant
𝑉𝑓
𝑊 = න 𝑃𝑑𝑉
𝑉𝑖
• Pressure is not constant, so it has to be expressed in a form
that will reflect what happens in the system
Given: ideal gas, therefore
𝑃𝑉 = 𝑛𝑅𝑇
𝑛𝑅𝑇
𝑃=
𝑉𝑓 𝑉
𝑛𝑅𝑇
𝑊=න 𝑑𝑉
𝑉𝑖 𝑉
35
• No reaction takes place in the system therefore mole, 𝑛 is constant;
• T is constant;
• R is a gas constant
𝑉𝑓
𝑑𝑉
𝑊 = 𝑛𝑅𝑇 න
𝑉𝑖 𝑉
𝑉𝑓
𝑊 = 𝑛𝑅𝑇 ln
𝑉𝑖

36
• Since mole is not changing, the number of moles can be calculated by
using the initial condition.
• Apply the ideal gas equation,
𝑃𝑖 𝑉𝑖 200 × 103 × 0.1
𝑛= =
𝑅𝑇 8.314 × 300
𝑛 = 0.00802 𝑘𝑚𝑜𝑙
0.2
𝑊 = 0.00802 × 8.314 × 300 × ln
0.1
𝑊 = 13.86𝑘𝐽

37
Electrical energy
• Electrical, and the mechanical forms of energy, are included in the
work term in an energy balance. Electrical energy will only be
significant in energy balances on electrochemical processes.
• Potential energy, Kinetic energy, Internal energy, and Enthalpy are the
forms of energy that can be possessed by a system.
• Energy is transferred either as heat or work. A system does not
contain “heat”, but the transfer of heat or work to a system changes
its internal energy.

38
• Recall: The dimension of energy is
𝑚. 𝐿2
𝐸= 2
𝜃
• The corresponding unit in SI is
𝑘𝑔.𝑚2
𝐸= = 𝑁. 𝑚 = 𝐽
𝑠2
• For the English system, the British Thermal Unit (BTU) is used.
Sometimes, the thermochemical calorie (cal) is also used.

39