ChE313 Chemical Engineering Thermodynamics Unit II.

First Law of Thermodynamics | 1

Unit II

First Law of Thermodynamics

Contents of Unit II.

2.1 Review: Conservation of Energy
2.2 System and Surroundings
2.3 Thermodynamic Change
2.4 Work and Force
2.4.1 Work
2.4.2 Heat
2.5 First Law of Thermodynamics
2.6 Thermodynamic State and Path Functions
2.6.1 State Functions
2.6.2 Path Functions
2.7 Energy Balance for Closed Systems
2.8 Reversible and Irreversible Change
2.9 Constant-V and Constant-P Processes
2.9.1 Internal energy and Heat Capacity at Constant-V Process
2.9.2 Enthalpy and Heat Capacity at Constant-P Process
2.10 Mass and Energy Balances for Open Systems
2.10.1 Measure of Flow
2.10.2 Mass Balance for Open Systems
2.10.3 General Energy Balance
2.10.4 Energy Balances for Steady-State Flow Processes
2.10.5 Flow Calorimeter

At the end of the unit, the students shall be able to:

1. Discuss the concept and difference between the system and the surroundings.
2. Discuss the concept of the first law of thermodynamics.
3. Discuss concept of thermodynamic change and differentiate state and path functions.
4. Discuss the concept and calculate thermodynamic quantities such as work, heat, enthalpy,
kinetic-, potential-, and internal energy.
5. Establish mass and energy balances for open and closed systems and perform necessary
calculations.
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 2

2.1 Review: Conservation of Energy

The work performed can be recovered by carrying out the reverse process and returning the body to its initial
condition. If the work done on a body in accelerating it or in elevating it can be subsequently recovered, then the body
by virtue of its velocity or elevation contains the ability or capacity to do work. Both kinetic- and potential-energy
changes are equal to the work done in producing them. It must be noted that work is energy in transit and is never
regarded as residing in a body. It is converted into another form of energy.

When the work is done by or on the system, energy is

transferred between the system and the surrounding. In contrast,
the kinetic- and potential-energy reside with the system and
measured with reference to the surroundings.

Example
An elevator with a mass of 2,500 𝑘𝑔 rests at a level 10 𝑚 above the base of an elevator shaft. It is raised to 100 𝑚
above the base of the shaft, where the cable holding it breaks. The elevator falls freely to the base of the shaft and
strikes a strong spring. The spring is designed to bring the elevator to rest and, by means of a catch arrangement, to
hold the elevator at the position of maximum spring compression. Assuming the entire process to be frictionless, and
taking 𝑔 = 9.8 𝑚 𝑠 −2 , calculate:
a. The potential energy of the elevator in its initial position relative to the base of the shaft.
b. The work done in raising the elevator.
c. The potential energy of the elevator in its highest position relative to the base of the shaft.
d. The velocity and kinetic energy of the elevator just before it strikes the spring.
e. The potential energy of the compressed spring.
f. The energy of the system consisting of the elevator and spring (1) at the start of the process, (2) when the
elevator reaches its maximum height, (3) just before the elevator strikes the spring, (4) after the elevator has
come to rest.

Solution
Step 1. Consider below assumptions
Subscript 1 = Initial conditions
Subscript 2 = Conditions when the elevator is at its highest position
Subscript 3 = Conditions just before the elevator strikes the spring
Subscript 4 = Conditions when elevator compressed the spring

Step 2. Calculate the unknown

(a) Potential Energy at point 1
𝐸𝑝1 = 𝑚𝑧1 𝑔 = (2500 𝑘𝑔)(10 𝑚)(9.8 𝑚 𝑠 −2) = 245,000 𝑘𝑔 𝑚2𝑠 −2 = 245,000 𝑁 ∙ 𝑚 = 245,000 𝐽

(b) Work at point 1

𝑧2 𝑧2
𝑊 = ∫ 𝐹 𝑑𝑙 = ∫ 𝑚𝑔 𝑑𝑙 = 𝑚𝑔(𝑧2 − 𝑧1 ) where 𝐹 = 𝑚𝑔
𝑧1 𝑧1

𝑊 = 𝑚𝑔(𝑧2 − 𝑧1 ) = (2500 𝑘𝑔)(9.8 𝑚 𝑠 −2)(100 − 10 𝑚) = 2,205,000 𝐽

(c) Potential Energy at point 2

𝐸𝑝2 = 𝑚𝑧2 𝑔 = (2500 𝑘𝑔)(100 𝑚)(9.8 𝑚 𝑠 −2) = 2,450,000 𝐽 where 𝑊 = 𝐸𝑝 − 𝐸𝑝
2 1

(d) Velocity and Kinetic Energy at point 3

Step d.1 Consider conservation of mechanical energy from point 2 to 3
∆𝐸𝑘2→3 + ∆𝐸𝑝2→3 = 0

(𝐸𝑘3 − 𝐸𝑘2 ) + (𝐸𝑝3 − 𝐸𝑝2 ) = 0

(𝐸𝑘3 − 0) + (0 − 𝐸𝑝2 ) = 0
𝐸𝑘3 = 𝐸𝑝2 = 2,450,000 𝐽 From calculations in (c)
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 3

Step d.2 Calculate velocity at point 3

1
𝐸𝑘3 = 𝑚𝑣32
2
2𝐸𝑘3 2(2,450,000 𝑘𝑔 𝑚2𝑠 −2 )
𝑢32 = =
𝑚 2,500 𝑘𝑔
𝑢3 = 44.27 𝑚/𝑠

(e) Potential Energy at Point 4

Consider conservation of mechanical energy from point 3 to 4
Mechanical energy between spring and
∆𝐸𝑘3→4 + ∆𝐸𝑝3→4 = 0 elevator : ∆𝐸𝑝 (𝑠𝑝𝑟𝑖𝑛𝑔) = ∆𝐸𝑘 (𝑒𝑙𝑒𝑣𝑎𝑡𝑜𝑟)

(𝐸𝑘4 − 𝐸𝑘3 ) + (𝐸𝑝4 − 𝐸𝑝3 ) = 0

(0 − 𝐸𝑘3 ) + (𝐸𝑝4 − 0) = 0
𝐸𝑘3 = 𝐸𝑝4
𝐸𝑘3 = 𝐸𝑝4 = 2,450,000 𝐽

(f) Energy of the system (elevator and spring)

𝑃𝑜𝑖𝑛𝑡 , 𝑃𝑎𝑡ℎ 𝐸𝑃 / 𝐸𝐾 𝑊 𝑇𝑜𝑡𝑎𝑙
1 245,000 245,000
1→2 2,205,000
2 245,000 2,205,000 2,450,000 System consists of elevator and spring
2→3 0 𝐸 = 𝐸𝑠𝑦𝑠 = 2,450,000 𝐽
3 2,450,000 2,450,000
3→4 0
4 2,450,000 2,450,000

2.2 System and Surroundings

The body of assemblage on which attention is focused is called the system. All else
is called the surroundings. The state is determined when a measurement or scientific
theory provides a complete description of a physical system. The thermodynamic
variables (T, P, V, N) collectively specify the macroscopic or thermodynamic state of a
thermodynamic system.

The molecular state energy E is conserved, constant over time, if the system is
isolated. An isolated system is one that has neither mechanical nor thermal contact
with its surroundings.

In reality, contact between system and surroundings allows for changes not only of the molecular state of the
system but also its thermodynamic state and that of the surroundings. Treating surroundings as an individual system,
the surroundings has its own thermodynamic variables and quantities (𝑋𝑠𝑢𝑟𝑟 ). Unlike the subsystems, the system and
surrounding are treated unequal. The system plus surroundings form the total system (𝑋𝑡𝑜𝑡 = 𝑋 + 𝑋𝑠𝑢𝑟𝑟 ) that is isolated
where conservation laws are applied and the boundary is flexible.

2.3 Thermodynamic Change

Thermodynamic systems in equilibrium indicates that there is no change in external factors. When external
factors change, the thermodynamic state also changes making independent variables change its value. Refer to the
initial thermodynamic state as “state A” and final thermodynamic quantities as “state B” denoted with “i” and “f”
subscript, respectively. The change in thermodynamic quantity can be represented as ΔX = (𝑋𝑓 − 𝑋𝑖 ). A
thermodynamic change required a specification of what both independent variables are doing. Often, thermodynamic
changes occur under the special condition that one of the variable is held constant. The constant or fixed variable is
usually chosen as one of the two independent variables.
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 4

Example:
Gas expansion at constant pressure

Variable Initial value Final value Change

𝑃 𝑃𝑖 = 𝑃 𝑃𝑓 = 𝑃 Δ𝑃 = 0
𝑉 𝑉𝑖 𝑉𝑓 Δ𝑉 = (𝑉𝑓 − 𝑉𝑖 )

2.4 Work and Force

2.4.1 Work
For an infinitesimal thermodynamic change, initial state A and final state B are arbitrarily close (𝑃𝑓 , 𝑉𝑓 ) ≈
(𝑃𝑖 , 𝑉𝑖 ) where (𝑃𝑓 , 𝑉𝑓 ) = (𝑃𝑖 + 𝑑𝑃, 𝑉𝑖 + 𝑑𝑉 ). Thus, Δ𝑃 → 𝑑𝑃 and ΔV → 𝑑𝑉 which is the same for all other state function
quantities i.e. ΔX → 𝑑𝑋. Under any infinitesimal thermodynamic change, the revised first law of thermodynamics
can be represented as 𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊.

According to physics, the infinitesimal work dW done when moving a macroscopic object against an opposing
force 𝐹𝑠𝑢𝑟 and represented as by 𝑑𝑊 = −𝐹𝑠𝑢𝑟 𝑑𝑧 where 𝑑𝑧 is the infinitesimal change in the object’s position. In
thermodynamic terms, the opposing force is imparted by the surroundings and the macroscopic object is the movable
dividing wall. It is usually regarded in the piston-cylinder apparatus where work is observed in the change in volume
of a fluid. Referring to Fig. 2.1, the “system” is the gas inside the cylinder. The piston serves as the movable dividing
wall; as part of the surroundings, it also provides the opposing force, 𝐹𝑠𝑢𝑟 (and the surroundings pressure, 𝑃𝑠𝑢𝑟 ).
Expansion is in the vertical direction. The resultant infinitesimal work is negative; work is done by the system on
the surroundings.

Figure 2.1. Expansion work for piston-cylinder apparatus. Source: B. Poirier (2014)

𝑑𝑊 = −𝐹𝑠𝑢𝑟 𝑑𝑧 Infinitesimal work

𝑉 𝐹
𝑑𝑊 = −(𝑃𝑠𝑢𝑟 𝐴) 𝑑 where 𝑃 =
𝐴
𝐴
𝑑𝑊 = −𝑃𝑠𝑢𝑟 𝑑𝑉
𝑉𝑓 Work where 𝑃𝑠𝑢𝑟 (𝑉) is a pressure of the surrounding as a
− ∫ 𝑃𝑠𝑢𝑟 (𝑉) 𝑑𝑉 function of volume and specifies the path from A to B
𝑊 =
𝑉𝑖 𝑊 𝑖𝑛 𝑁 𝑚 −1 𝑜𝑟 𝐽 (SI unit) | 𝑊 𝑖𝑛 𝑓𝑡 𝑙𝑏𝑓 (English unit)

The applied force and its displacement are in the same direction when the fluid is compressed wherein the
piston moves into the cylinder. The minus sign is attributed to the negative change in volume (Δ𝑉 < 0) thus, the
work is positive. While in expansion process, the applied force and its displacement are in the opposite direction.
The volume change is positive (Δ𝑉 > 0) thus, the work is negative.

The following are two conditions required to any thermodynamic process to exhibit nonzero work: (1) a change
in the system volume, 𝑉; and (2) a nonzero surroundings pressure, 𝑃𝑠𝑢𝑟, against which the expansion/compression
takes place. Without condition 1, there is no macroscopic motion and therefore no work. Without condition 2, there
is free expansion/compression but no work.

2.4.2 Heat
At the molecular scale, heat is the transfer of molecular kinetic energy across a diathermic wall. Heat always
flow from a higher to a lower temperature and regarded as the driving force for the transfer of energy. Heat, like
work, is considered as energy in transit between the system and the surrounding and does not stored within a body.
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 5

At the macroscopic scale, it is defined as the energy left in a thermodynamic change and represented in below
equation.
𝑄 = Δ𝑈 − 𝑊 𝑄 : Heat | Δ𝑈 : Change in internal energy | 𝑊 : Work

When energy in the form of heat is added to a system, it is stored as kinetic and potential energy of the atoms
and molecules making up the system.

2.5 First Law of Thermodynamics

When the total system is isolated, 𝐸𝑡𝑜𝑡 is conserved. Similarly, 𝑈𝑡𝑜𝑡 = ⟨𝐸𝑡𝑜𝑡 ⟩ when internal state energy is ignored.
The total value of internal energy is equal to the of the values for each of its parts, i.e. 𝑈𝑡𝑜𝑡 = 𝑈 + 𝑈𝑠𝑢𝑟𝑟 .

First law of thermodynamics (total system) states that the energy of the total system is conserved under any
thermodynamic change. Energy assumes many forms, the total quantity of energy is constant, and when energy
disappears in one form it appears simultaneously in other forms.

The law is applied to a given process that occurs in a system which can be of any
size. Its boundaries may be real or imaginary, rigid or flexible. Moreover, the first law
also applies to the surrounding where the influence of the process is considered.
The first law requirement for any process is represent by below equation
∆𝐸𝑡𝑜𝑡 = ∆𝐸 + ∆𝐸𝑠𝑢𝑟 = 0 or Δ𝑋𝑡𝑜𝑡 = ΔX + Δ𝑋𝑠𝑢𝑟 ≠ 0
where ∆ signifies finite changes in the quantities such as internal energy, potential
energy, and kinetic energy.

In thermodynamics, heat and work represent energy in transit across the boundary dividing the system from its
surroundings, and are never stored or contained in the system. While kinetic-, potential-, and internal energy are
stored with matter.

2.6 Thermodynamic State and Path Functions

It can be noted from previous equations of internal energy that internal energy reflect the changes in the
thermodynamic state of the system as reflected by its thermodynamic properties such as temperature, pressure, and
density.
𝑁 𝑁
𝑚 2 2 2
𝑈 = ∑〈𝐸𝐾,𝑖 〉 = ∑ [〈 𝑣𝑥,𝑖 〉 + 〈 𝑣𝑦,𝑖 〉 + 〈 𝑣𝑧,𝑖 〉] Ideal gas of point particles
2
𝑖=1 𝑖=1

𝑘𝑇 𝑚 2 𝑚 2 𝑚 2
= 〈𝑣 〉 = 〈𝑣𝑦,𝑖 〉 = 〈𝑣𝑧,𝑖 〉 System in thermal equilibrium for all i
2 2 𝑥,𝑖 2 2

Noting that 𝑃𝑉 = 𝑛𝑅𝑇 = 𝑁𝑘𝑇 for ideal gas and based from the representation of ideal gas of point particles in
thermal equilibrium, we obtain 𝑈(𝑇, 𝑉 ) state function.
3 3
𝑈(𝑇, 𝑉 ) = 𝑁𝑘𝑇 = 𝑛𝑅𝑇 𝑈 (𝑇, 𝑉) state function for the ideal gas of point particles
2 2
𝑑 𝑈 (𝑇, 𝑉) state function for the ideal gas of point particles where 𝑑 is the
𝑈(𝑇, 𝑉 ) = 𝑛𝑅𝑇
2 total number of translational and rotational coordinates per molecule

Molecule Type and Number of Coordinates

Molecule type Translational Rotation Total (d)

Monoatomic (point, e.g. Ar) 3 0 3
Diatomic (linear, e.g. 𝑁2) 3 2 5
Polyatomic (nonlinear, e.g. 𝐻2𝑂) 3 3 6

Note that for ideal gases, the state function 𝑈(𝑇, 𝑉 ) depends only on the thermodynamic variable T, not on V. This
is due to the lack of intermolecular interactions where the distance r, and thus the molar volume 𝑉𝑚 have no effect on
the energy. For ideal gases, U and T are the same thermodynamic energy quantity where U is extensive and T is
intensive. For non-ideal cases, T relates only to molecular kinetic energy, whereas U also incorporates molecular
potential energy and depends on V. (Poirier)
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 6

2.6.1 State Functions

State functions are quantities that are independent of the history of the substance or the means, such as heating
or cooling, and compression or expansion, by which it reaches the given state. Fixing values of two of these properties
will fix the other properties in homogeneous pure substance thus, determines its thermodynamic state. A state
function such as specific internal energy U, is a property that always has a value and can be expressed
mathematically as a function of two quantities, from temperature, pressure, and density. These state functions are
associated as path endpoints.
𝑃2
∫ 𝑑𝑃 = 𝑃2 − 𝑃1 = ∆𝑃 The differential of a state function represents an
𝑃1 infinitesimal change in its value.
𝑉2 The equations show differential results in a finite
∫ 𝑑𝑉 = 𝑉2 − 𝑉1 = ∆𝑉 difference between two of its values.
𝑉1

2.6.2 Path Functions

The First Law of thermodynamics follow laws of conservation dealing with energy transfer between system and
surroundings. Mechanical contact leads to energy transfer in the form of work W and thermal contact leads to energy
transfer in the form of heat Q. This means of energy transfer revises the first law as represented by below equation:
Δ𝑈 = 𝑄 + 𝑊 where 𝑄𝑠𝑢𝑟𝑟 = −𝑄 | 𝑊𝑠𝑢𝑟𝑟 = −𝑊

Heat Q and work W quantities are not considered state functions (properties) but path functions
(thermodynamic processes) where energy changes occur in the surroundings. Unlike properties, these path functions
depend on the nature of the process and may be associated with areas rather than values of initial and final
properties.

∫ 𝑑𝑄 = 𝑄 Differential changes of heat and work are not changes,

but are infinitesimal amounts.

∫ 𝑑𝑊 = 𝑊 The equations show differential results in finite amounts.

Below figure (Fig. 2.2) shows gas expansion at constant P indicating state functions and path functions. The
system begins in the initial state A at (𝑃𝑖 = 𝑃, 𝑉𝑖 ) then undergoes a thermodynamic change to the final state B at
(𝑃𝑓 = 𝑃, 𝑉𝑓 ) following the constant pressure path as indicated.

Figure 2.2. Gas expansion at constant P. Source: B. Poirier (2014)

Example
A gas is confined in a cylinder by a piston. The initial pressure of the gas is 7 𝑏𝑎𝑟, and the volume is 0.10 𝑚3.
The piston is held in place by latches in the cylinder wall. The whole apparatus is placed in a total vacuum. What
is the energy change of the apparatus if the restraining latches are removed so that the gas suddenly expands to
double its initial volume, the piston striking other latches at the end of the process?
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 7

Solution
Step 1: Select the system

𝑆𝑦𝑠𝑡𝑒𝑚 = 𝐴𝑝𝑝𝑎𝑟𝑎𝑡𝑢𝑠 (𝑔𝑎𝑠, 𝑝𝑖𝑠𝑡𝑜𝑛, 𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟)

Step 2. Consider state and path function quantities between the system and the surroundings
𝑄 = Δ𝑈 − 𝑊
𝑊 = 0 No external force to move the system
0 = Δ𝑈 − 0 𝑄 = 0 No heat transferred between the system and the vacuum surrounding

Δ𝑈 = 0

Example
A gas is confined in a cylinder by a piston. The initial pressure of the gas is 7 𝑏𝑎𝑟, and the volume is 0.10 𝑚3.
The piston is held in place by latches in the cylinder wall. The apparatus is surrounded by air at atmospheric
pressure of 101.3 𝑘𝑃𝑎, what is the energy change of the apparatus? Assume the rate of heat exchange between the
apparatus and the surrounding air is slow compared with the rate at which the process occurs.

Solution
Step 1. Select the system

𝑆𝑦𝑠𝑡𝑒𝑚 = 𝐴𝑝𝑝𝑎𝑟𝑎𝑡𝑢𝑠 (𝑔𝑎𝑠, 𝑝𝑖𝑠𝑡𝑜𝑛, 𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟)

Step 2. Consider state and path function quantities between the system and the surroundings
2.1 Work
𝑊 = −𝐹 ∆𝑙 Work done by the system in pushing back the atmosphere

𝐹 : force at the back side of the piston, 𝐹 = 𝑃𝑎𝑡𝑚 𝐴

= −(𝑃𝑎𝑡𝑚 𝐴 )(Δ𝑉 𝑡 /𝐴)
Δ𝑙 : displacement of the piston, Δ𝑉 𝑡 = Δ𝑙 𝐴 → Δ𝑙 = Δ𝑉 𝑡 /𝐴

= −𝑃𝑎𝑡𝑚 ∆𝑉 𝑡
= −(101.3)(0.2 − 0.1) 𝑘𝑃𝑎 𝑚3
𝑊 = −10.13 𝑘𝑁 𝑚 ≈ −10.13 𝑘𝐽

2.2 Energy
∆𝐸 = 𝑄+𝑊 Assume 𝑄 = 0

= 0 − 10.13
The total energy of the system has decreased by an
∆𝐸 = −10.13 𝑘𝐽 amount equal to the work done on the surroundings.
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 8

Example
When a system is taken from state a to state b as shown in the
figure along path acb, 100 𝐽 of heat flows into the system and the system
does 40 𝐽 of work.
(a) How much heat flows into the system along path aeb if the work
done by the system is 20 𝐽?
(b) The system returns from b to a along path bda. If the work done
on the system is 30 𝐽, does the system absorb or liberate heat?
How much?

Solution
Step 1. Assume that the system changes only in its internal energy
𝑡
𝛥𝑈𝑎𝑏 = 𝑄+𝑊 Applicable to any path from a to b

Step 2. Calculate unknown based on the path

(a) Heat along path aeb
𝑡 = 𝑄𝑎𝑒𝑏 + 𝑊𝑎𝑒𝑏
∆𝑈𝑎𝑏
𝑄𝑎𝑐𝑏 + 𝑊𝑎𝑐𝑏 = 𝑄𝑎𝑒𝑏 + 𝑊𝑎𝑒𝑏 where ∆𝑈𝑎𝑏
𝑡
= 𝑄𝑎𝑐𝑏 + 𝑊𝑎𝑐𝑏

100 − 40 = 𝑄𝑎𝑒𝑏 − 20
𝑄𝑎𝑒𝑏 = 80 𝐽

(b) Heat along path bda

𝑡 = 𝑄𝑏𝑑𝑎 + 𝑊𝑏𝑑𝑎
∆𝑈𝑏𝑎
𝑡 = 𝑄𝑏𝑑𝑎 + 𝑊𝑏𝑑𝑎
−∆𝑈𝑎𝑏
−(100 − 40) = 𝑄𝑏𝑑𝑎 + 30
𝑄𝑏𝑑𝑎 = −90 𝐽 Heat is transferred from the system to the surroundings

2.7 Energy Balance for Closed Systems

A system is considered a closed system if the boundary of a system
does not permit the transfer of matter between the system and its
surroundings. Thus, its mass is constant.

There is no energy associated with matter is transported across the

boundary since there are no streams enter or leave a closed system. Thus,
all energy exchange between the closed system and its surroundings are
heat and work. The total energy change of the surroundings equals the
net energy transferred to or from it as heat and work.

Temperature 𝑇 and pressure 𝑃 are, principal thermodynamic coordinates for pure homogeneous fluids,
independent of the quantity of material and are known as intensive properties. While the properties that are dependent
of the quantity of material are called extensive properties such as total volume 𝑉 𝑡 and total internal energy 𝑈 𝑡.

For a homogeneous system, extensive properties can be represented by intensive properties such as below
quantities. Although 𝑉 𝑡 and 𝑈 𝑡 for a homogeneous system of arbitrary size are extensive properties, specific and molar
volume 𝑉 (or density) and specific and molar internal energy 𝑈 are intensive.
𝑉𝑡 = 𝑚𝑉 = 𝑛𝑉 𝑉 : Volume of a unit amount of material; 𝑉 𝑡 : Specific or molar properties

𝑈𝑡 = 𝑚𝑈 = 𝑛𝑈 𝑈 : Internal energy of a unit amount of material; 𝑈 𝑡 : Specific or molar properties

The total energy change of a closed system equals the net energy transferred into it as heat and work as
represented by below equation. The energy, heat, and work are regarded as positive quantities for transfer into the
system from the surroundings. While energy, heat, and work of the surroundings are negative quantities of the system.
𝐸 = 𝑄+𝑊 𝐸 : energy of the system | 𝑄 : heat of the system | 𝑊 : work of the system.

∆𝐸𝑠𝑢𝑟𝑟 = 𝑄𝑠𝑢𝑟 + 𝑊𝑠𝑢𝑟 𝑄𝑠𝑢𝑟𝑟 𝑊𝑠𝑢𝑟 refers to the heat and work of the surroundings

∆𝐸𝑠𝑢𝑟𝑟 = −𝑄 − 𝑊
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 9

For closed systems with process where internal energy of the system changes. Below represents relationship of
these changes with heat and work considering 𝑛 moles.
∆𝐸 = 𝑄 + 𝑊
∆𝑈 𝑡 = 𝑄 + 𝑊
Total internal energy of the system involving Total internal energy of the system involving
finite changes considering 𝑛 moles differential changes considering 𝑛 moles

∆(𝑛𝑈 𝑡 ) = 𝑛 ∆𝑈 = 𝑄 + 𝑊 𝑑(𝑛𝑈 𝑡 ) = 𝑛 𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊
𝑡 For 𝑛 = 1 𝑡 For 𝑛 = 1
∆𝑈 = 𝑄+𝑊 𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊

Example
Water flows over a waterfall 100 𝑚 in height. Take 1 𝑘𝑔 of the water as the system, and assume that is does not
exchange energy with its surroundings.
a. What is the potential energy of the water at the top of the falls with respect to the base of the falls?
b. What is the kinetic energy of the water just before it strikes bottom?
c. After the 1 𝑘𝑔 of water enters the stream below the falls, what change has occurred in its state?

Solution
Step 1. Consider given and basis
∆𝐸𝑠𝑢𝑟 = 0

Step 2. Consider first law of thermodynamics

∆𝐸 + ∆𝐸𝑠𝑢𝑟 = 0
∆𝐸 + 0 = 0 No exchange of energy with the surrounding

∆𝐸 = ∆𝑈 + ∆𝐸𝑘 + ∆𝐸𝑝

Step 3. Calculate the unknown

(a) Potential energy of 1 𝑘𝑔 water at the top of the falls
𝐸𝑝 = 𝑚𝑔𝑧 = (1 𝑘𝑔)(100 − 0𝑚)(9.8066 𝑚 𝑠 −2) = 980.66 𝐽

(b) Kinetic energy of 1 𝑘𝑔 water before is strikes the base

∆𝐸𝑘 + ∆𝐸𝑝 = 0

(𝐸𝑘2 − 𝐸𝑘1 ) + (𝐸𝑝2 − 𝐸𝑝1 ) = 0 Let 𝐸𝑘1 = 𝐸𝑝2 = 0

(𝐸𝑘2 − 0) + (0 − 𝐸𝑝1 ) = 0
𝐸𝑘2 − 𝐸𝑝1 = 0
𝐸𝑘2 = 𝐸𝑝1 = 980.66 𝐽

(c) Energy below the falls

Step c.1 Determine change in energy
∆𝐸 = 0
∆𝑈 + ∆𝐸𝑘 + ∆𝐸𝑝 = 0
∆𝑈 + ∆𝐸𝑘 + 0 = 0
∆𝑈 = −∆𝐸𝑘 = −(𝐸𝑘,3 − 𝐸𝑘,2 )
∆𝑈 = 𝐸𝑘2 − 𝐸𝑘3 Assume stream velocity is small, 𝐸𝑘3 ≈ 0

∆𝑈 = 𝐸𝑘2 = 980.66 𝐽

Step c.2 Determine change in temperature

Δ𝑇 Δ𝐸
= Note: 4,184 𝐽/𝑘𝑔 to increase temperature to 1℃
Δ𝑇𝑟𝑒𝑓 Δ𝐸𝑟𝑒𝑓
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 10

980.66 𝐽/𝑘𝑔
Δ𝑇 = (1℃)
4,184 𝐽/𝑘𝑔
Temperature increases assuming no heat transferred
Δ𝑇 = 0.234 ℃
between the system and the surroundings

For a closed system undergoing the same change in state by several processes, experiment shows that the amounts
of heat and work required differ for different processes, but that the sum Q + W is the same for all processes. This is
the basis for identification of internal energy as a state function. The same value of ∆𝑈 𝑡 is given regardless of the
process, provided only that the change in the system is between the same initial and final states.

2.8 Reversible and Irreversible Change

Thermodynamic change can either be reversible or irreversible. When the system is in equilibrium at every step
along the path from A to B with 𝑃 = 𝑃𝑠𝑢𝑟 throughout, the change is considered to be reversible. In practice, reversible
implies that external factors change very slowly that the system readjust incrementally throughout the process. Its
direction can be reversed at any point by an infinitesimal change in external conditions. While when the system is far
from equilibrium for at least part of the path from A to B is considered to be irreversible. The change occurs after a
sudden external change that move the system far from equilibrium. The system then undergoes a spontaneous
thermodynamic change until a new equilibrium state is reached.

Reversible vs Irreversible Change

Reversible Irreversible
Equilibrium throughout Equilibrium at endpoints only
Path on equation of state Path far from equation of state
Slow external factor change Fast external factor change
Not spontaneous Spontaneous
Maximum work Less than maximum work
Figure 2.3. Reversible and irreversible
isothermal paths. Source: B. Poirier (2014)

Note that the reversible path generates more work (larger |W|) than does the irreversible path. This is always
the case for a true ΔV > 0 expansion; of all physically realizable paths from A to B, the reversible path yields maximum
work. To expand a gas, one must first ease up on 𝑃𝑠𝑢𝑟 , and then allow the system to increase V on its own (thereby
restoring equilibrium). Hence, all real isothermal expansion paths lie below the reversible path indicated in Fig. 2.3.
To compress a gas, one first increases 𝑃𝑠𝑢𝑟 , and then allows V to decrease. Thus, all real compression paths lie above
the reversible path in Fig. 2.3.

Below are system requirements for the application of work done in reversible process:
1. The system be no more than infinitesimally displaced from a state of internal equilibrium, characterized by
uniformity of temperature and pressure.
2. The system be no more than infinitesimally displace from mechanical equilibrium with its surroundings.

𝑑𝑊 = −𝑃𝑠𝑢𝑟 𝑑𝑉
𝑉𝑓
System’s work applied to mechanically reversible process
𝑊 = − ∫ 𝑃𝑠𝑢𝑟 (𝑉 ) 𝑑𝑉
which met the requirements
𝑉𝑖

The reversible work as the limiting value may be combined with an appropriate efficiency to yield a reasonable
approximation to the work of an actual process.

There are reversible and irreversible expansions, for gases that are either ideal or non-ideal. Some expansions are
isothermal (constant T); others are isobaric (constant 𝑃𝑠𝑢𝑟 ). There are also free (𝑊 = 0) and adiabatic 𝑄 = 0) gas
𝑉 1 𝑉𝑓
expansions. For reversible isothermal expansion of ideal gas, we obtain 𝑊 = −𝑛𝑅𝑇 ∫𝑉 𝑓 ( ) 𝑑𝑉 = −𝑛𝑅𝑇 ln ( ).
𝑖 𝑉 𝑉𝑖

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 gas pressure of 14 𝑏𝑎𝑟. The
initial gas volume is 0.03 𝑚3. The external force on the piston is reduced gradually, and the gas expands isothermally
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 11

as its volume doubles. If the volume of the gas is related to its pressure so that the products 𝑃𝑉 𝑡 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 initial value instead of being
gradually reduced?

Solution
(a) Work done by the gas in moving the external force making the gas expand where the volume doubles
Step 1. Determine basis
Reversible isothermal expansion of ideal gas.

Step 2. Set the working equation

𝑉2𝑡
𝑊 = − ∫ 𝑃 𝑑𝑉 𝑡 Applicable to mechanically reversible process
𝑉1𝑡

𝑉2𝑡
𝑑𝑉 𝑡
= −𝑘 ∫ If 𝑃𝑉 𝑡 = 𝑘, then 𝑃 = 𝑘/𝑉 𝑡
𝑉1𝑡 𝑉𝑡

𝑉2𝑡
𝑊 = −𝑘 ln
𝑉1𝑡

Step 3. Determine the values of the components in the working equation

(a) 𝑘 = 𝑃𝑉 𝑡 = 𝑃1𝑉1𝑡 = (14 × 105)(0.03) = 42,000 𝐽

(b) 𝑉1𝑡 = 0.03 𝑚3 𝑉2𝑡 = 2(𝑉1𝑡 ) = 0.06 𝑚3

Step 4. Calculate work

𝑉2𝑡 0.06
𝑊 = −𝑘 ln = −42,000 ln = −29,112 𝐽
𝑉1𝑡 0.03

Step 5. Calculate final pressure 𝑃2

𝑘 = 𝑃2𝑉2𝑡
𝑘 42,000
𝑃2 = = = 700,000 𝑃𝑎 ≈ 7 𝑏𝑎𝑟
𝑉2𝑡 0.06

(b) Work if the external force were suddenly reduced to half its initial value
Step 1. Determine the basis
Isothermal expansion of ideal gas.

Step 2. Set the working equation

𝑉2𝑡
𝑊 = − ∫ 𝑃 𝑑𝑉 𝑡
𝑉1𝑡

𝑊 = 𝑃(𝑉2𝑡 − 𝑉1𝑡 )

Step 3. Determine the values of the components in the working equation

(a) 𝑃 = 7 × 105 𝑃𝑎

(b) 𝑉2𝑡 = 0.06 𝑚3 𝑉1𝑡 = 0.03 𝑚3

Step 4. Calculate work for the process (irreversible)

𝑉2𝑡
𝑊 = − ∫ 𝑃 𝑑𝑉 𝑡 = −(7 × 105)(0.06 − 0.03) = −21,000 𝐽
𝑉1𝑡

Step 5. Process efficiency

𝜂𝑖𝑟𝑟𝑒𝑣 21,000
𝜂𝑟𝑒𝑣 = = = 0.721 ≈ 72.1%
𝜂𝑟𝑒𝑣 29,112
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 12

Example
The piston/cylinder arrangement shown contains nitrogen gas trapped below
the piston at a pressure of 7 𝑏𝑎𝑟. The piston is held in place by latches. The space
above the piston is evacuated. A pan is attached to the piston rod and a mass m of
45 𝑘𝑔 is fastened to the pan. The piston, piston rod, and pan together have a mass
of 23 𝑘𝑔. The latches holding the piston are release, allowing the piston to rise
rapidly until it strikes the top of the cylinder. The distance moved by the piston is
0.5 𝑚. The local acceleration of gravity is 9.8 𝑚 𝑠 −2. Discuss the energy changes that
occur because of this process.

Solution

Step 1. Determine basis

• Irreversible nonflow process
• System = gas
• Change of potential energy in the surroundings consider piston, rod, pan, mass
• Change of internal energy in the surroundings consider piston, rod, cylinder
• 𝑊 = ∫ 𝑃′ 𝑑𝑉 𝑡 ( 𝑃 ′ : pressure exerted by the gas on the piston)

Step 2. Calculate the energy changes

Δ𝐸𝑠𝑦𝑠 + ΔEsur = 0
𝑡 𝑡 = 0
∆𝑈𝑠𝑦𝑠 + (∆𝑈𝑠𝑢𝑟𝑟 + ∆𝐸𝑃𝑠𝑢𝑟𝑟 )
𝑡 𝑡 = −∆𝐸𝑃𝑠𝑢𝑟𝑟
∆𝑈𝑠𝑦𝑠 + ∆𝑈𝑠𝑢𝑟
𝑡 𝑡
∆𝑈𝑠𝑦𝑠 + ∆𝑈𝑠𝑢𝑟 = −𝑚𝑔ℎ
𝑡 𝑡
∆𝑈𝑠𝑦𝑠 + ∆𝑈𝑠𝑢𝑟 = −(45 + 23)(98)(0.5)
𝑡
∆𝑈𝑠𝑦𝑠 𝑡
+ ∆𝑈𝑠𝑢𝑟 = −333.2 𝑁 𝑚 ≈ −333.2 𝐽 𝑡
𝑈𝑠𝑦𝑠 , ∆𝑈𝑠𝑢𝑟
𝑡
cannot be determined

2.9 Constant-V and Constant-P Processes

The energy balance of n moles of a homogeneous fluid in a closed system undergoing a mechanically reversible
process is represented in below equation.
𝑑 (𝑛𝑈 ) = 𝑑𝑄 + 𝑑𝑊 𝑄 : Total heat | 𝑊 : Total work

Considering work for a mechanically reversible,

𝑑 (𝑛𝑈 ) = 𝑑𝑄 − 𝑃 𝑑(𝑛𝑉 ) closed-system process 𝑑𝑊 = −𝑃 𝑑(𝑛𝑉 )

The smaller the temperature change in a body caused by the transfer of a given quantity of heat, the greater its
capacity. Heat capacity is a process-dependent quantity rather than a state function.
𝑑𝑄
𝐶 = Heat capacity mathematical definition
𝑑𝑇

2.9.1 Internal Energy and Heat Capacity at Constant-Volume Process

For process occurring at closed systems with constant total volume, the work is zero since n and V are both
constant. Thus, the heat transferred in a mechanically reversible, constant volume, closed system process equals
the internal energy change of the system.
𝑑(𝑛𝑈 ) = 𝑑𝑄 + 𝑑𝑊 𝑄 : Total heat ; 𝑊 : Total work

For closed system at constant V

𝑑(𝑛𝑈 ) = 𝑑𝑄
𝑛 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ; 𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ; 𝑑𝑊 = 0

𝑑𝑄 = 𝑑(𝑛𝑈 )
𝑄 = 𝑛 ∆𝑈 For mechanically reversible, constant-volume, closed-system process
3
𝑄 = 𝑛 ∆𝑈 = 𝑛𝑅Δ𝑇 For an ideal gas under constant volume conditions
2

The heat capacity at constant volume, 𝐶𝑣 , is defined to be the partial derivative of 𝑈(𝑇, 𝑉 ) with respect to T at
constant V as represented on below equation. Note that 𝐶𝑉 is a state function and an extensive quantity.
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 13

𝜕𝑈 Heat capacity at constant volume where 𝑈 is molar or specific internal

𝐶𝑉 = ( )|
𝜕𝑇 𝑉 energy, and T (varying) and V (fixed) are the two independent variables

3
𝐶𝑉 = 𝑛𝑅 Heat capacity at constant volume for an ideal gas
2

Below calculates change in internal energy considering the heat capacity at constant volume for an ideal gas:
𝑑𝑈 = 𝑑𝑄 = 𝐶𝑉 𝑑𝑇
𝑇𝑓
Heat for an ideal gas under mechanically reversible,
ΔU = 𝑄 = ∫ 𝐶𝑉 (𝑇 ) 𝑑𝑇
𝑇𝑖
constant volume conditions

2.9.2 Enthalpy and Heat Capacity at Constant-Pressure Process

The heat transferred in a mechanically reversible, constant pressure change of state, closed system process
equals the enthalpy change of the system.
𝑑(𝑛𝑈 ) = 𝑑𝑄 + 𝑑𝑊 𝑄 : Total heat | 𝑊 : Total work

𝑑(𝑛𝑈 ) = 𝑑𝑄 − 𝑃 𝑑(𝑛𝑉 ) At constant P change of state

𝑑𝑄 = 𝑑(𝑛𝑈 ) + 𝑃 𝑑(𝑛𝑉 )
𝑑𝑄 = 𝑑(𝑛𝑈 ) + 𝑑(𝑛𝑃𝑉 )
𝑑𝑄 = 𝑑[𝑛(𝑈 + 𝑃𝑉)] where 𝐻 : Enthalpy is mathematically defined as 𝐻 ≡ 𝑈 + 𝑃𝑉

𝑑𝑄 = 𝑑(𝑛𝐻 ) For closed system at constant P

𝑄 = 𝑛 ∆𝐻 For mechanically reversible, constant-pressure, closed-system process

Enthalpy H is an extensive state function with dimensions of energy that is closely related to U. It naturally
varies with T and P. It is represented by below equation.
𝐻 = 𝑈 + 𝑃𝑉
𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉)
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝐻 = [𝑑𝑄 − 𝑃𝑑𝑉 ] + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝐻 = 𝑑𝑄 + 𝑉𝑑𝑃
∆𝐻 = 𝑄

Note that an infinitesimal change, proceeding on the equation of state away from an initial state that is in
equilibrium, is necessarily reversible. Thus, 𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊 = 𝑑𝑄 − 𝑃𝑠𝑢𝑟 𝑑𝑉 = 𝑑𝑄 − 𝑃𝑑𝑉.

The heat capacity at constant pressure, 𝐶𝑃 , is defined to be the partial derivative of H(T, P) with respect to T at
constant P as represented on below equation.
𝜕𝐻 Heat capacity at constant pressure where 𝐻 is molar or specific enthalpy,
𝐶𝑃 = ( )|
𝜕𝑇 𝑃 and T (varying) and V (fixed) are the two independent variables

5
𝐶𝑃 = 𝑛𝑅 Heat capacity at constant pressure for an ideal gas
2

Below calculates change in enthalpy considering the heat capacity at constant pressure for an ideal gas:
𝑑𝐻 = 𝑑𝑄 = 𝐶𝑃 𝑑𝑇
𝑇𝑓
Heat for an ideal gas under mechanically reversible,
ΔH = 𝑄 = ∫ 𝐶𝑃 (𝑇 ) 𝑑𝑇
constant pressure conditions
𝑇𝑖

Example
Calculate ∆𝑈 and ∆𝐻 for 1 𝑘𝑔 of water when it is vaporized at the constant temperature of 100 ℃ and the constant
pressure of 101.33 𝑘𝑃𝑎. The specific volumes of liquid and vapor water at these conditions are 0.00104 and
1.673 𝑚3𝑘𝑔−1. For this change, heat in the amount of 2,256.9 𝑘𝐽 is added to the water.

Solution
Step 1. Determine the basis
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 14

• As water evaporates, its volume expands. Therefore, the process is expansion.

• System constant T at 100 ℃ and P at 101.33 𝑘𝑃𝑎
• 1 mol of water occupies the system

Step 2. Consider heat at constant P

𝑄 = 𝑛 Δ𝐻 = 2,256.9 𝑘𝐽 For 𝑛 = 1

Step 3. Relate Δ𝐻 to Δ𝑈
∆𝐻 = ∆𝑈 + ∆(𝑃𝑉) Rearrange

∆𝑈 = ∆𝐻 − ∆(𝑃𝑉)
∆𝑈 = ∆𝐻 − 𝑃 ∆𝑉 At constant P

∆𝑈 = 2,256.9 𝑘𝐽 − [101.33 𝑘𝑃𝑎 × (1.673 − 0.001 𝑚3)]

∆𝑈 = 2,256.9 − 169.4 𝑘𝐽 𝑘𝑃𝑎 ∙ 𝑚3 = 𝑘𝑁 ∙ 𝑚 −2 ∙ 𝑚3 = 𝑘𝐽

∆𝑈 = 2,087.5 𝑘𝐽

Example
Air at 1 𝑏𝑎𝑟 and 298.15 𝐾 (25 ℃) is compressed to 5 𝑏𝑎𝑟 and 298.15 𝐾 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 the heat and work requirements and ∆𝑈 and ∆𝐻 of the air for each path. The heat capacities for air may
be assumed independent of temperature with values 𝐶𝑉 = 20.78 and 𝐶𝑃 = 29.10 𝐽 𝑚𝑜𝑙−1 𝐾 −1 . Assume also for air that
𝑃𝑉/𝑇 is a constant, regardless of the changes it undergoes. At 298.15 𝐾 and 1 𝑏𝑎𝑟 the molar volume of air is
0.02479 𝑚3 𝑚𝑜𝑙−1 .

Solution
Step 1. Set assumptions and basis
• Air undergoes mechanically reversible process
• At 𝑇 = 298.15 𝐾 and 𝑃 = 1 𝑏𝑎𝑟, 𝑉𝑚 = 0.02479 𝑚3 𝑚𝑜𝑙−1

Step 2. Consider state functions in air compression

(a) Initial conditions
𝑃1 = 1 𝑏𝑎𝑟
𝑉1 = 0.02479 𝑚3 𝑚𝑜𝑙−1
(b) Final conditions
𝑃2 = 5 𝑏𝑎𝑟
𝑃1 1
𝑉2 = 𝑉1 = 0.02479 ( ) = 0.004958 𝑚3 For 𝑃1 𝑉1 = 𝑃2 𝑉2
𝑃2 5
(c) Intermediate condition
𝑇′ 𝑉2
=
𝑇1 𝑉1
𝑉2 0.004958
𝑇′ = 𝑇1 ( ) = 298.15 ( ) = 59.63 𝐾
𝑉1 0.02479

Step 3. Calculate unknown

(a) Q and W when air was subjected to cooling at constant-P followed by heating at constant-V
Step a.1 Cooling at constant-P
𝑄1 = ∆𝐻1 Heat at constant P

𝑄1 = 𝐶𝑃 Δ𝑇
𝑄1 = (29.10 𝐽/𝑚𝑜𝑙 𝐾 )(59.63 − 298.15 𝐾 )
𝑄1 = −6,941 𝐽
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 15

Δ𝑈1 = Δ𝐻1 − Δ(𝑃𝑉) = ∆𝐻 − 𝑃 ∆𝑉

Δ𝑈1 = −6,941 − [(1 × 105)(0.004958 − 0.02479)]
Δ𝑈1 = −4,958 𝐽

Step a.2 Heating at constant-V

𝑄2 = ∆𝑈2
𝑄2 = 𝐶𝑉 Δ𝑇
𝑄2 = (20.78 𝐽/𝑚𝑜𝑙 𝐾 )(298.15 − 59.63 𝐾 )
𝑄2 = 4,958 𝐽

Step a.3 Heat and work for the whole process

𝑄𝑎 = 𝑄1 + 𝑄2 = −6,941 + 4,958 = −1,983 𝐽
Δ𝑈𝑎 = Δ𝑈1 + ∆𝑈2 = −4,958 + 4,958 = 0

Step a.4 Work for the whole process

Δ𝑈𝑎 = 𝑄𝑎 + 𝑊𝑎
0 = −1,983 + 𝑊𝑎
𝑊𝑎 = 1,983 𝐽

Step a.5 Enthalpy for the whole process

∆𝐻𝑎 = ∆𝑈𝑎 + ∆(𝑃𝑉) For 𝑇1 = 𝑇2 , 𝑃1 𝑉1 = 𝑃2 𝑉2 . Thus ∆(𝑃𝑉) = 0

∆𝐻𝑎 = ∆𝑈𝑎 = 0

(b) Q and W when air was subjected to heating at constant-V followed by cooling at constant-P
Step b.1 Heating at constant-V
𝑄2 = ∆𝑈2
𝑇 ′ 𝑃1 5
𝑄2 = 𝐶𝑉 ∆𝑇 = ⟶ 𝑇 ′ = 298.15 ( ) = 1,490.75 𝐾
𝑇1 𝑃2 1

𝑄2 = (20.78 𝐽/𝑚𝑜𝑙 𝐾 )(1,490.75 − 298.15 𝐾 )

𝑄2 = 24,788 𝐽

Step b.2 Cooling at constant-P

𝑄2 = ∆𝐻2
𝑄2 = 𝐶𝑃 Δ𝑇
𝑄2 = (29.10 𝐽/𝑚𝑜𝑙 𝐾 )(298.15 − 1,490.75 𝐾 )
𝑄2 = −34,703 𝐽

∆𝑈2 = ∆𝐻 − ∆(𝑃𝑉 ) = ∆𝐻 − 𝑃 ∆𝑉
∆𝑈2 = −34,703 − [(5 × 105)(0.004958 − 0.02479)]
∆𝑈2 = −24,788 𝐽

Step b.3 Heat and work for the whole process

𝑄𝑏 = 𝑄1 + 𝑄2 = 24,788 − 34,703 = −9,915 𝐽
∆𝑈𝑏 = Δ𝑈1 + ∆𝑈2 = 24,788 − 24,788 = 0

Step b.4 Work for the whole process

Δ𝑈𝑏 = 𝑄𝑏 + 𝑊𝑏
0 = −9,915 + 𝑊𝑏
𝑊𝑏 = 9,915 𝐽
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 16

Step b.5 Enthalpy for the whole process

∆𝐻𝑏 = ∆𝑈𝑏 + ∆(𝑃𝑉 ) For 𝑇1 = 𝑇2 , 𝑃1 𝑉1 = 𝑃2 𝑉2 . Thus ∆(𝑃𝑉 ) = 0

∆𝐻𝑏 = ∆𝑈𝑏 = 0

Example
Calculate the internal energy and enthalpy changes that occur when air is changed from an initial state of 40 ℉
and 10 𝑎𝑡𝑚, where its molar volume is 36.49 𝑓𝑡 3𝑙𝑏𝑚𝑜𝑙−1, to a final state of 140 ℉ and 1 𝑎𝑡𝑚. Assume for air that 𝑃𝑉/𝑇
is constant and that 𝐶𝑉 = 5 and 𝐶𝑃 = 7 𝐵𝑡𝑢 𝑙𝑏𝑚𝑜𝑙−1 ℉−1 .

Solution
Step 1. Set assumptions and basis
• 1 𝑙𝑏𝑚𝑜𝑙 of air undergoes two-step mechanically reversible process
Step 1 : Cooling at constant-V to the final P
Step 2 : Heating at constant-P to the final T
• 𝑃𝑉/𝑇 = 𝑘𝑇 is constant

Step 2. Consider state functions in the process

(a) Initial conditions
𝑇1 = 40 + 459.67 = 499.67 𝑅
𝑃1 = 10 𝑎𝑡𝑚
𝑉1 = 36.49 𝑓𝑡 3𝑙𝑏𝑚𝑜𝑙−1
(b) Final conditions
𝑇2 = 140 + 459.67 = 599.67 𝑅
𝑃2 = 1 𝑎𝑡𝑚
𝑃1𝑇2 10 × 599.67 𝑃1 𝑇2 𝑃2 𝑇1
𝑉2 = 𝑉1 ( ) = 36.49 ( ) = 437.93 𝑓𝑡 3 For constant PV/T : =
𝑃2𝑇1 1 × 499.67 𝑉2 𝑉1

(c) Intermediate condition

𝑇′ 𝑃1
=
𝑇1 𝑃2
𝑃1 1
𝑇′ = 𝑇1 ( ) = 499.67 ( ) = 49.97 𝑅
𝑃2 10

Step 3. Consider temperature changes in the two state functions

∆𝑇𝑎 = 49.97 − 499.67 = −449.70 (𝑅)
∆𝑇𝑏 = 599.67 − 49.97 = 549.70 (𝑅)

Step 4. Consider the changes in the state functions on the two-step process
Step 4.1 Cooling at constant-V to the final P
𝑄𝑎 ∆𝑈𝑎
𝑄𝑎 = ∆𝑈𝑎 = 𝐶𝑉 ∆𝑇𝑎
∆𝑈𝑎 = (5 𝐵𝑡𝑢 𝑙𝑏𝑚𝑜𝑙−1 ℉−1 )(−449.70) × 1 𝑙𝑏𝑚𝑜𝑙
∆𝑈𝑎 = −2,248.5 𝐵𝑡𝑢

∆𝐻𝑎 = ∆𝑈𝑎 + 𝑉 ∆𝑃𝑎

𝑓𝑡 3 2.7195 𝐵𝑡𝑢
= −2,248.5 𝐵𝑡𝑢 + [(36.49 ) (1 − 10) × ]
𝑙𝑏𝑚𝑜𝑙 1 𝑎𝑡𝑚 𝑓𝑡 3
∆𝐻𝑎 = −3,141.6 𝐵𝑡𝑢

Step 4.2 Heating at constant-P to the final T

𝑄𝑏 ∆𝐻𝑏
𝑄𝑏 = ∆𝐻𝑏 = 𝐶𝑃 ∆𝑇𝑏
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 17

∆𝐻𝑏 = (7 𝐵𝑡𝑢 𝑙𝑏𝑚𝑜𝑙−1 ℉−1 )(549.70) × 1 𝑙𝑏𝑚𝑜𝑙

∆𝐻𝑏 = 3,847.9 𝐵𝑡𝑢

∆𝑈𝑏 = ∆𝐻𝑏 − 𝑃 ∆𝑉𝑏

2.7195 𝐵𝑡𝑢
= 3,847.9 𝐵𝑡𝑢 − [(1 𝑎𝑡𝑚)(437.93 − 36.49) × ]
1 𝑎𝑡𝑚 𝑓𝑡 3
∆𝑈𝑏 = 2,756.2 𝐵𝑡𝑢

Step 5. Calculate changes is state functions for the whole process

∆𝑈 = ∆𝑈𝑎 + ∆𝑈𝑏 = −2,248.5 + 2,756.2 = 507.7 𝐵𝑡𝑢
∆𝐻 = ∆𝐻𝑎 + ∆𝐻𝑏 = −3,141.6 + 3,847.9 = 706.3 𝐵𝑡𝑢

2.10 Mass and Energy Balances for Open Systems

The law of mass and energy conservation is applied to all process, both in open and closed systems. The open
system includes closed system as special case.
2.10.1 Measures of Flow
Open systems are characterized by flowing streams; there are four common measures of flow:
(a) Mass flowrate, 𝑚̇ 𝑚̇ = 𝑀𝑛̇ = 𝑢𝐴𝜌
(b) Molar flowrate, 𝑛̇ 𝑛̇ = 𝑢𝐴𝜌 𝐴 : Cross-sectional area of a conduit ; 𝜌 : Specific
or molar density ; 𝑢 : Average speed of a stream
(c) Volumetric flowrate, 𝑞 𝑞 = 𝑢𝐴 in the direction normal to 𝐴

(d) Velocity, 𝑢 𝑢 = 𝑞/𝐴

Example
Liquid n-hexane flows at a rate of 𝑚̇ = 0.75 𝑘𝑔 𝑠 −1 in a pipe with inside diameter 𝐷 = 5 𝑐𝑚. What are 𝑞, 𝑛̇ , and
𝑢? What would these quantities be for the same 𝑚̇ if 𝐷 = 2 𝑐𝑚? Assume for liquid n-hexane that 𝜌 = 659 𝑘𝑔 𝑚 −3.

Solution
Pipe inside diameter, 𝐷 𝐷 = 5 𝑐𝑚 𝐷 = 2 𝑐𝑚

Mass flowrate, 𝑚̇ 𝑚̇ = 0.75 𝑘𝑔 𝑠 −1 𝑚̇ = 0.75 𝑘𝑔 𝑠 −1

Volumetric flowrate, 𝑞 𝑚̇ 𝑚̇
𝑞 = 𝑢𝐴 = ( )𝐴 𝑞 = 𝑢𝐴 = ( )𝐴
𝐴𝜌 𝐴𝜌
𝑚̇ 0.75 𝑘𝑔 𝑠 −1 𝑚̇ 0.75 𝑘𝑔 𝑠 −1
𝑞= = 𝑞= = = 0.00114 𝑚3 𝑠 −1
𝜌 659 𝑘𝑔 𝑚−3 𝜌 659 𝑘𝑔 𝑚−3
𝑞 = 0.00114 𝑚 3 𝑠 −1 𝑞 = 0.00114 𝑚 3 𝑠 −1

Molar flowrate, 𝑛̇ 𝑚̇ (0.75 𝑘𝑔 𝑠 −1)(1 × 103 𝑔 𝑘𝑔−1) 𝑚̇ (0.75 𝑘𝑔 𝑠 −1)(1 × 103 𝑔 𝑘𝑔−1 )
𝑛̇ = = 𝑛̇ = =
𝑀 86.177 𝑔 𝑚𝑜𝑙−1 𝑀 86.177 𝑔 𝑚𝑜𝑙−1
𝑛̇ = 8.703 𝑚𝑜𝑙 𝑠 −1 𝑛̇ = 8.703 𝑚𝑜𝑙 𝑠 −1

Velocity, 𝑢 𝑞 𝑞 𝑞 𝑞
𝑢= = 𝑢= =
𝐴 𝜋𝐷 2/4 𝐴 𝜋𝐷 2/4
0.00114 𝑚3 𝑠 −1 0.00114 𝑚3 𝑠 −1
𝑢= 𝑢=
(𝜋/4)(5 × 10−2 𝑚)2 (𝜋/4)(2 × 10−2 𝑚)2
𝑢 = 0.582 𝑚 𝑠 −1 𝑢 = 3.63 𝑚 𝑠 −1

2.10.2 Mass Balance for Open Systems

The region of space identified for analysis of open systems is called a control volume; it is separated from its
surroundings by a control surface. The fluid within the control volume is the thermodynamic system for which mass
and energy balances are written.
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 18

The control volume is separated from its surroundings by an

extensible control surface. Flow rates 𝑚̇1 and 𝑚̇2 are going in the control
volume while 𝑚̇3 is directed out. Considering mass is conserved, the mass
balance can be expressed as:

𝑑𝑚𝐶𝑉 /𝑑𝑡 : rate of change of mass within the control

𝑑𝑚𝐶𝑉 volume | ∆(𝑚̇ )𝑓𝑠 : net rate of flow of mass into the
+ ∆(𝑚̇)𝑓𝑠 = 0 control volume | ∆ : Difference between exit and
𝑑𝑡
entrance flows | Subscript 𝑓𝑠 : Flowing streams

Figure 2.4 Schematic diagram of a 𝑑𝑚𝐶𝑉 Mass balance equation or continuity equation
+ ∆(𝜌𝑢𝐴)𝑓𝑠 = 0 where ∆(𝑚̇ )𝑓𝑠 = 𝑚̇3 − 𝑚̇1 − 𝑚̇2
control volume. Source: Smith et al. (2005) 𝑑𝑡

The flow process characterized as steady state implies that the conditions within the control volume do not
change with time. The control volume contains a constant mass of fluid, and the accumulation term is zero.
At steady state, the mass flowing in is equal to the
∆(𝜌𝑢𝐴)𝑓𝑠 = 0
mass flowing out

𝜌2𝑢2 𝐴2 − 𝜌1 𝑢1 𝐴1 = 0 One stream flowing in, one stream flowing out

𝜌2 𝑢2𝐴2 𝜌1 𝑢1 𝐴1
𝑚̇ = 𝑐𝑜𝑛𝑠𝑡
𝑢1 𝐴1 𝑢2 𝐴2 𝑢𝐴
𝑚̇ = = =
𝑉1 𝑉2 𝑉

2.10.3 General Energy Balance

Like conservation of mass, energy is conserved implying the rate of change of energy within the control volume
is equal to the net rate of energy transfer into the control volume. Each unit mass of a stream carries internal,
potential, and kinetic forms of energy and all that contribute energy change of the system.
Energy of each stream;
1 𝑈 : internal energy | 𝑢 : average velocity of the stream | 𝑧
𝐸𝑡𝑜𝑡 = 𝑈 + 𝑢2 + 𝑧𝑔 :elevation above a datum level | 𝑔 : local acceleration of gravity
2
Rate of energy transported by each steam
1
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 = (𝑈 + 𝑢2 + 𝑧𝑔) 𝑚̇
2
Net energy transported into the system by the flowing stream
1
𝑁𝑒𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 = −∆ [(𝑈 + 𝑢2 + 𝑧𝑔) 𝑚̇] where −∆= 𝑖𝑛 − 𝑜𝑢𝑡
2 𝑓𝑠

Rate of energy accumulations within the control volume

𝑑(𝑚𝑈 )𝐶𝑉 1
= −∆ [(𝑈 + 𝑢2 + 𝑧𝑔) 𝑚̇] + 𝑄̇ + 𝑊̇ 𝑄̇ : Heat flow ; 𝑊̇ : Rate of work
𝑑𝑡 2 𝑓𝑠

Considering a control volume with one

entrance and one exit as shown in below
figure, each stream has its corresponding
properties. The path quantities Q and W, in
any or several forms, acting in the control
volume were also included (refer to Fig. 2.5).

Work : 𝑊 = 𝑃𝑉

Work rate : 𝑊̇̇ = (𝑃𝑉 )𝑚̇

Net work : 𝑊̇𝑛𝑒𝑡 = −∆[(𝑃𝑉 )𝑚̇]𝑓𝑠

Figure 2.5 Control volume with one entrance and one exit
Source: Smith et al. (2005)

The rate of energy accumulation within the control volume may be represented by below equation considering
shaft work and the exerted work in expansion or compression of the control volume (refer to Fig. 2.5).
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 19

𝑑(𝑚𝑈 )𝐶𝑉 1 Rate of energy accumulations

= −∆ [(𝑈 + 𝑢2 + 𝑧𝑔) 𝑚̇] + 𝑄̇ + 𝑊̇
𝑑𝑡 2 𝑓𝑠 within the control volume

𝑑(𝑚𝑈 )𝐶𝑉 1 Rate of energy accumulations

= −∆ [(𝑈 + 𝑢2 + 𝑧𝑔) 𝑚̇] + 𝑄̇ − ∆[(𝑃𝑉)𝑚̇]𝑓𝑠 + 𝑊̇
𝑑𝑡 2 𝑓𝑠 considering forms of work

𝑑(𝑚𝑈 )𝐶𝑉 1
= −∆ [( 𝑢2 + 𝑧𝑔) 𝑚̇] − ∆[(𝑈 + 𝑃𝑉 )𝑚̇]𝑓𝑠 + 𝑄̇ + 𝑊̇ where 𝐻 = 𝑈 + 𝑃𝑉
𝑑𝑡 2 𝑓𝑠

𝑑(𝑚𝑈 )𝐶𝑉 1
= −∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇] + 𝑄̇ + 𝑊̇
𝑑𝑡 2 𝑓𝑠

𝑑(𝑚𝑈 )𝐶𝑉 1
+ ∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇ ] = 𝑄̇ + 𝑊̇
𝑑𝑡 2 𝑓𝑠

𝑑(𝑚𝑈 )𝐶𝑉 Center of mass of the control volume is

+ ∆[(𝐻 + 0 + 0)𝑚̇]𝑓𝑠 = 𝑄̇ + 𝑊̇ stationary. Thus ∆𝐸𝐾 = 0 and ∆𝐸𝑃 = 0
𝑑𝑡
𝑑(𝑚𝑈 )𝐶𝑉
+ ∆(𝐻𝑚̇ )𝑓𝑠 = 𝑄̇ + 𝑊̇
𝑑𝑡

Example
Relate energy balance equation of open system to closed system.

Solution
𝑑(𝑚𝑈 )𝐶𝑉
+ ∆(𝐻𝑚̇)𝑓𝑠 = 𝑄̇ + 𝑊̇ For open system
𝑑𝑡
𝑑(𝑚𝑈 )𝐶𝑉 = 𝑄̇ 𝑑𝑡 + 𝑊̇ 𝑑𝑡 ∆(𝐻𝑚̇ )𝑓𝑠 = 0 for closed system
𝑡2 𝑡2
∆(𝑚𝑈 )𝐶𝑉 = ∫ 𝑄̇ 𝑑𝑡 + ∫ 𝑊̇ 𝑑𝑡
𝑡1 𝑡1

∆𝑈 𝑡 = 𝑄+𝑊 For closed system

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.

Solution
Step 1. Set assumptions and basis
• Control volume : Tank with single entrance
• 𝑊̇ = 0 since no expansion, no stirring/mixing, or shaft work
• Negligible kinetic- and potential-energy changes
• 𝑄̇ = 0 neglecting heat transfer between the gas and the tank

Step 2. Consider energy balance between gas and tank

𝑑(𝑚𝑈 )𝐶𝑉 1
+ ∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇ ] = 𝑄̇ + 𝑊̇ Tank with single entrance
𝑑𝑡 2 𝑓𝑠

𝑑(𝑚𝑈 )𝐶𝑉
+ ∆(𝐻𝑚̇ )𝑓𝑠 = 0 ∆𝐸𝐾 = 0 | ∆𝐸𝑃 = 0 | 𝑄̇ = 0 | 𝑊̇ = 0
𝑑𝑡
𝑑(𝑚𝑈 )𝐶𝑉
− [(𝐻1 − 𝐻2 )𝑚̇ ]𝑓𝑠 = 0
𝑑𝑡
𝑑(𝑚𝑈 )𝐶𝑉 𝑑𝑚𝑡𝑎𝑛𝑘
− [(𝐻1 ) ] = 0 Considering stream at the entrance only
𝑑𝑡 𝑑𝑡 𝑓𝑠
Subscript prime (′) : entrance stream
𝑑(𝑚𝑈 )𝑡𝑎𝑛𝑘 𝑑𝑚𝑡𝑎𝑛𝑘
− 𝐻′ = 0 Minus sign : denotes 𝑖𝑛 − 𝑜𝑢𝑡
𝑑𝑡 𝑑𝑡 where 𝑚̇ ′ = 𝑑𝑚𝑡𝑎𝑛𝑘 /𝑑𝑡
∆(𝑚𝑈)𝑡𝑎𝑛𝑘 − 𝐻′∆𝑚𝑡𝑎𝑛𝑘 = 0
′(
[𝑚2𝑈2 − 𝑚1 𝑈1 ] − [𝐻 𝑚2 − 𝑚1 )] = 0
𝑚2 𝑈2 − 𝑚1 𝑈1 = 𝐻 ′(𝑚2 − 𝑚1 ) 𝑚1 = 0 (initial condition)
′
𝑚2𝑈2 = 𝑚2𝐻
𝑈2 = 𝐻′
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 20

Example
An insulated, electrically heated tank for hot water contains 190 𝑘𝑔 of liquid water at 60 ℃ when a power outage
occurs. If water is withdrawn from the tank at a steady rate of 𝑚̇ = 0.2 𝑘𝑔 𝑠 −1 , how long will it take for the
temperature of the water in the tank to drop from 60 to 35 ℃? Assume cold water enters the tank at 10 ℃, and
negligible heat losses from the tank. For liquid water let 𝐶𝑉 = 𝐶𝑃 = 𝐶, independent of 𝑇 and 𝑃.

Solution
Step 1. Set assumptions and basis
Basis:
• Control volume : Tank with single entrance and single exit
• 𝑊̇ = 0 since no expansion, no stirring/mixing, or shaft work
• 𝑄̇ = 0 neglecting heat transfer
• Δ𝐸𝐾 = 0 , Δ𝐸𝑃 = 0 neglecting changes in kinetic and potential energies
• Heat capacity 𝐶𝑉 = 𝐶𝑃 = 𝐶 and independent of T and P
Assumptions:
• Assume perfect mixing of the contents of the tank. The properties of water leaving the tank
(subscript 2) is equal to the properties of water inside the tank (no subscript).
• Assume mass conservation is applied: 𝑚̇𝑖𝑛 = 𝑚̇𝑜𝑢𝑡 and 𝑚𝐶𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Step 2. Consider energy balance in the control volume

𝑑(𝑚𝑈 )𝐶𝑉 1 No subscript : water in the tank
+ ∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇] = 𝑄̇ + 𝑊̇
𝑑𝑡 2 𝑓𝑠 Subscript 1 : water entering in the tank

𝑑(𝑚𝑈 )𝐶𝑉
+ ∆[(𝐻 + 0 + 0)𝑚̇]𝑓𝑠 = 0
𝑑𝑡
𝑑𝑈
𝑚 + 𝑚̇ (𝐻 − 𝐻1 ) = 0 Note: Δ𝐻 = 𝐶𝑃 Δ𝑇 → 𝐻 − 𝐻1 = 𝐶(𝑇 − 𝑇1 )
𝑑𝑡
𝑑𝑈
𝑚 + 𝑚̇𝐶(𝑇 − 𝑇1 ) = 0
𝑑𝑡
𝑑𝑈 𝑑𝑇
𝑚 + 𝑚̇𝐶 = 0
𝑑𝑡 𝑑𝑡
𝑚 𝑑𝑇
𝑑𝑡 = − At 𝑡 = 0, 𝑇 = 𝑇0
𝑚̇ 𝑇 − 𝑇1
𝑚 𝑇 − 𝑇1
𝑡 = − ln ( )
𝑚̇ 𝑇0 − 𝑇1
190 35 − 10
𝑡 = − ln ( )
0.2 60 − 10
𝑡 = 658.5 𝑠 ≈ 11 𝑚𝑖𝑛

2.10.4 Energy Balances for Steady-State Flow Processes

A steady-state flow process implies a zero-accumulation term, 𝑑(𝑚𝑈 )𝐶𝑉 /𝑑𝑡. At steady-state, the flow rates are
not constant rather the mass of the system within the control volume is constant. There are no changes occur with
time in the properties of the fluid within the control volume nor at its entrances and exits. The steady state does not
necessarily imply steady flow. No expansion of the control volume is possible and only the shaft work is considered
at steady-state process flow. The energy balance for this process is represented by the simplified equation below:
𝑑(𝑚𝑈 )𝐶𝑉 1 Rate of energy accumulations
+ ∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇] = 𝑄̇ + 𝑊̇
𝑑𝑡 2 𝑓𝑠 within the control volume

1
∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇] = 𝑄̇ + 𝑊̇𝑆 At steady-state, steady-flow process
2 𝑓𝑠

1 For control volume with one

∆ (𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇ = 𝑄̇ + 𝑊̇𝑆 entrance and one exit
2
1 𝑄̇ 𝑊̇𝑆
∆ (𝐻 + 𝑢2 + 𝑧𝑔) = +
2 𝑚̇ 𝑚̇
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 21

1 At steady-state, steady-flow process

∆ (𝐻 + 𝑢2 + 𝑧𝑔) = 𝑄 + 𝑊𝑠
with one entrance and one exit
2
∆𝑢2
∆𝐻 + + 𝑔∆𝑧 = 𝑄 + 𝑊𝑠 For SI unit
2
∆𝑢2 𝑔
∆𝐻 + + ∆𝑧 = 𝑄 + 𝑊𝑆 For English unit
2𝑔𝑐 𝑔𝑐
∆𝐻 = 𝑄 + 𝑊𝑆 For negligible Δ𝐸𝐾 and Δ𝐸𝑃

2.10.5 Flow Calorimeter

Below figure shows a schematic diagram for a simple flow calorimeter. It includes an electric resistance heater
immersed in a flowing fluid with no shaft work entering the system. The design implies negligible kinetic- and
potential-energy changes due to minimal velocity and elevation changes from section 1 to section 2. The rate of heat
transfer to the fluid is determined from the resistance of the heater and the current passing through it.

Figure 2.6 Flow calorimeter. Source: Smith et al. (2005)

Applying the conservation of energy considering a steady-state, steady flow in the illustrated calorimeter
simplifies the energy balance equation. It is applied due to the changes of state, for which enthalpy is independent
of the location of the zero point.
1
∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇ ] = 𝑄̇ + 𝑊̇𝑆 At steady-state, steady-flow process
2 𝑓𝑠

∆𝐻 = 𝑄 For negligible Δ𝐸𝐾 , Δ𝐸𝑃 and no shaft work

𝐻2 − 𝐻1 = 𝑄

Example
The following data are taken from a flow calorimeter with water as the test fluid:
𝐹𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 4.15 𝑔 𝑠 −1 𝑡1 = 0 ℃ 𝑡2 = 300 ℃ 𝑃2 = 3 𝑏𝑎𝑟
𝑅𝑎𝑡𝑒 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑎𝑑𝑑𝑖𝑡𝑖𝑜𝑛 𝑓𝑟𝑜𝑚 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 ℎ𝑒𝑎𝑡𝑒𝑟 = 12,740 𝑊
The water is completely vaporized in a process. Calculate the enthalpy of steam at 300 ℃ and 3 𝑏𝑎𝑟 based on 𝐻 = 0
for liquid water at 0 ℃.

Solution
Step 1. Set assumptions and basis
Basis:
• Minimal changes of elevation Δ𝑧 and velocity Δ𝑢2 in flow calorimeter
• Δ𝐸𝐾 = 0 , Δ𝐸𝑃 = 0 negligible changes in kinetic and potential energies
• Ws = 0 no shaft work
• H1 = 0 enthalpy of liquid water at 𝑡1 = 0℃
• 𝑚̇ = 4.15 𝑔 𝑠 −1 amount of water flowing
Assumption:
• The system is at steady-state, steady flow process

Step 2. Consider the energy balance at steady-state, steady flow process

ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 22

1
∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇] = 𝑄̇ + 𝑊̇𝑆
2 𝑓𝑠

𝑚̇∆𝐻 = 𝑄
𝑚̇ (𝐻2 − 𝐻1 ) = 𝑄 Working equation

Step 3. Calculate enthalpy from the working equation

𝑚̇(𝐻2 − 𝐻1 ) = 𝑄̇ Consider amount of fluid flowing

𝑄̇
𝐻2 = 𝑊 = 𝐽/𝑠
𝑚̇
12,740 𝐽 𝑠 −1
𝐻2 =
4.15 𝑔 𝑠 −1
𝐻2 = 3,070 𝐽 𝑔−1

Example
Air at 1 𝑏𝑎𝑟 and 25 ℃ enters a compressor at low velocity, discharges at 3 𝑏𝑎𝑟, and enters a nozzle in which it
expands to a final velocity of 600 𝑚 𝑠 −1 at the initial conditions of pressure and temperature. If the work of
compression is 240 𝑘𝐽 𝑝𝑒𝑟 𝑘𝑔 of air, how much heat must be removed during compression?

Solution
Step 1. Set basis and assumptions
Basis:
• Fluid undergoes reversible process since it returns to its initial conditions of T and P
• ∆𝐻 = 0 since the process is reversible
Assumptions:
• The system is at steady-state, steady flow process [𝑑(𝑚𝑈 )𝐶𝑉 /𝑑𝑡 = 0]
• Δ𝐸𝑃 = 0 negligible change in potential energy
• 𝐸𝐾,1 = 0 neglect initial kinetic energy

Step 2. Consider the energy balance at steady-state, steady-flow process

1
∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇] = 𝑄̇ + 𝑊̇𝑆 ∆𝐻 = 0 , Δ𝐸𝑃 = 0
2 𝑓𝑠

1
[ (𝑢22 − 𝑢12)] = 𝑄 + 𝑊𝑠 𝐸𝐾,1 = 0
2 𝑓𝑠

1 2
𝑄 = 𝑢 − 𝑊𝑠 Working equation
2 2

Step 3. Calculate heat from the working equation

1 2
𝑄 = 𝑢 − 𝑊𝑠
2 2
1 𝑚 2 𝑘𝑔 𝑘𝐽
𝑄 = [ (600 ) × ] − [240 ]
2 𝑠 𝑘𝑔 𝑘𝑔
𝑄 = −60 𝑘𝐽 𝑘𝑔−1

Example
Water at 200 ℉ is pumped from a storage tank at the rate of 50 𝑔𝑎𝑙 𝑚𝑖𝑛−1 . The motor for the pump supplies
work at the rate of 2 ℎ𝑝. The water goes through a heat exchanger, giving the heat at the rate of 40,000 𝐵𝑡𝑢 𝑚𝑖𝑛−1,
and is delivered to a second storage tank at an elevation of 50 𝑓𝑡 above the first tank. What is the temperature of
the water delivered to the second tank?

Solution
Step 1. Set assumptions
Assumptions:
• The system is at steady-state, steady flow process [𝑑(𝑚𝑈 )𝐶𝑉 /𝑑𝑡 = 0]
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 23

• 𝑢1 = 0 and 𝑢2 = 0 velocities of water in the storage tanks are negligible

• Δ𝐸𝐾 = 0 since velocities of water are negligible

Step 2. Consider the energy balance at steady-state, steady flow process

1
∆ [(𝐻 + 𝑢2 + 𝑧𝑔) 𝑚̇] = 𝑄̇ + 𝑊̇𝑆 Δ𝐸𝐾 = 0
2 𝑓𝑠

𝑔
∆𝐻 + ∆𝑧 = 𝑄 + 𝑊𝑠
𝑔𝑐
𝑔
∆𝐻 = 𝑄 + 𝑊𝑠 − ∆𝑧 Working equation
𝑔𝑐

Step 3. Determine values of the components of the working equation

(a) Properties of water
𝑚̇ = 𝑞×𝜌
𝑔𝑎𝑙 1𝑓𝑡 3 𝑙𝑏𝑚
= (50 × ) (60.1 3 ) 𝜌𝐻2 𝑂 = 60.1 𝑙𝑏𝑚 /𝑓𝑡 3 at 𝑇 = 200℉
𝑚𝑖𝑛 7.48 𝑔𝑎𝑙 𝑓𝑡
𝑚̇ = 402 𝑙𝑏𝑚 𝑚𝑖𝑛−1
(b) Heat
𝑄̇
𝑄 =
𝑚̇
𝐵𝑡𝑢 1
= (40,000 )( )
𝑚𝑖𝑛 402 𝑙𝑏𝑚 𝑚𝑖𝑛 −1
𝑄 = −99.50 𝐵𝑡𝑢 𝑙𝑏𝑚 −1
(c) Shaft work
𝑊̇𝑆
𝑊𝑆 =
𝑚̇
42.41 𝐵𝑡𝑢 ∙ 𝑚𝑖𝑛−1 1
= (2 ℎ𝑝 × )( )
1 ℎ𝑝 402 𝑙𝑏𝑚 𝑚𝑖𝑛 −1
𝑊𝑆 = 0.21 𝐵𝑡𝑢 𝑙𝑏𝑚 −1
(d) Potential energy
𝑔
𝐸𝑃 = ∆𝑧
𝑔𝑐
32.174 𝑓𝑡 · 𝑠 −1 0.947831 𝐵𝑡𝑢 · 𝑠 −1
= [( 2
) (50 𝑓𝑡)] ×
32.174 𝑙𝑏𝑚 · 𝑓𝑡 /(𝑙𝑏𝑓 · 𝑠 ) 737.562 𝑓𝑡 · 𝑙𝑏𝑓 · 𝑠 −1
𝐸𝑃 = 0.06 𝐵𝑡𝑢 𝑙𝑏𝑚 −1

Step 4. Calculate change in enthalpy from the working equation

𝑔
∆𝐻 = 𝑄 + 𝑊𝑠 − ∆𝑧
𝑔𝑐
= −99.50 + 0.21 + 0.06 𝐵𝑡𝑢 𝑙𝑏𝑚 −1
∆𝐻 = −99.35 𝐵𝑡𝑢 𝑙𝑏𝑚 −1

Step 5. Determine enthalpy in the second tank

Step 5.1 Determine initial enthalpy from steam table 𝑇 = 200℉
ChE313 Chemical Engineering Thermodynamics Unit II. First Law of Thermodynamics | 24

Figure 2.7 Saturated Steam Table in English units. Source: Smith et al. (2005)
𝐻1 = 168.05 𝐵𝑡𝑢 𝑚𝑖𝑛−1 At 𝑇 = 200℉

Step 5.2 Relate initial enthalpy to the calculated change of enthalpy

∆𝐻 = 𝐻2 − 𝐻1
−99.35 = 𝐻2 − 168.05
𝐻2 = 68.70 𝐵𝑡𝑢/ 𝑙𝑏𝑚

Step 6. Determine temperature in the second tank

Step 6.1 Relate the calculated enthalpy to temperature based from steam table
At 𝑇 = 100℉ 𝐻 = 68.00 𝐵𝑡𝑢/ 𝑙𝑏𝑚
At 𝑇 = 102℉ 𝐻 = 70.00 𝐵𝑡𝑢/ 𝑙𝑏𝑚

Figure 2.8 Saturated Steam Table in English units. Source: Smith et al. (2005)
Step 6.2 Determine temperature based from the calculated enthalpy
102 − 100 ℉ 70.00 − 68.00 𝐵𝑡𝑢/ 𝑙𝑏𝑚
=
𝑇2 − 100 ℉ 68.70 − 70.00 𝐵𝑡𝑢/ 𝑙𝑏𝑚
𝑇2 = 100.70 ℉

References:
[1] Smith, J.M., Van Ness, H.C., Abbott, M.M. (2005). Introduction to Chemical Engineering Thermodynamics (7 th
Ed.). McGraw-Hill. ISBN 007-124795-5
[2] Poirier, B. (2014). A Conceptual Guide to Thermodynamics. John Wiley & Sons, Ltd. UK
[3] Perry, R.H., & Green, D.W. (2008). Perry’s Chemical Engineer’s Handbook (8th Ed.). McGraw-Hill Companies,
Inc.