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Chapter 9. Energy Balances
Table 9.1. Previously Defined Terminology That Pertains to Energy Balances
Term Definition or explanation
Boundary Hypothetical perimeter used to define what a system is.
Closed system A system in which mass is not exchanged with the surroundings
(non-flow
system)
Open system A system in which interchange of mass occurs with the surroundings.
(flow system)
Property An observable or calculable characteristic of a system, such as temperature
or
enthalpy.
State Conditions of the system, such as the values of the temperature or pressure.
Steady state The accumulation in a system is zero, the flows in and out are constant, and
the
properties of the system are invariant.
Unsteady state Not steady state
Surrounding Everything outside a system.
System The quantity of matter or region of space chosen for analysis.
Adiabatic system A process in which no heat transfer occurs (Q = 0).
Isobaric sys. Describes a system for which the pressure is invariant during a process.
Isochoric sys. Describes a system for which the volume is invariant during a process.
Isothermal sys. Describes a system in which the temperature is invariant during a process.
9.2. Types of Energy to Be Included in Energy Balances
Energy itself is often defined as the capacity to do work or transfer heat, a fuzzy concept. It is
easier to understand specific types of energy. Two things energy is not are (a) some sort of
invisible fluid and (b) something that can be measured directly.
9.2.1. Heat (Q)
Heat, Q, when used in the general energy balance, Equation (9.17), as a single term, is the net
amount of heat transferred to or from the system over a fixed time interval. A process may
involve more than one specified form of heat transfer, of course, the sum of which is Q.
Figure 9.5. Heat transfer is energy that crosses the system boundary because of a temperature difference.
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9.2. Types of Energy to Be Included in Energy Balances
9.2.2. Work (W)
The next type of energy we discuss is work (W). Work is a term that has wide usage in everyday
life (such as “I am going to work”) but has a specialized meaning in connection with energy
balances. Work is a form of energy that represents a transfer of energy between the system and
surroundings. Work cannot be stored. Work is a path variable. Work is positive when the
surroundings perform work on the system. Work is negative when the system performs work on
the surroundings
• Mechanical work: Work that occurs because of a mechanical force that moves the boundary
of a system.
𝒔𝒕𝒂𝒕𝒆𝟐
𝑾 = 𝒔𝒕𝒂𝒕𝒆𝟏 𝑭𝒅𝒔 where F is an external force
Ex. Suppose that an ideal gas at 300 K and 200 kPa is enclosed in a cylinder by a frictionless (ideal) piston,
and the gas slowly forces the piston so that the volume of gas expands from 0.1 to 0.2 m3. Examine Figure
E9.2a. Calculate the work done by the gas on the piston (the only part of the system boundary that moves) if
two different paths are used to go from the initial state to the final state.
Path A: The expansion occurs at constant pressure (isobaric) (p = 200 kPa).
Path B: The expansion occurs at constant temperature (isothermal) (T = 300 K).
9.2. Types of Energy to Be Included in Energy Balances
𝒑𝑽 𝟐𝟎𝟎 𝒌𝒑𝒂 𝟎. 𝟏𝒎𝟑 𝒌𝒈 𝒎𝒐𝒍 . 𝑲
𝒑𝒗 = 𝒏𝑹𝑻 ⇒≫ 𝒏 = = = 𝟎. 𝟎𝟎𝟖𝟎𝟐 𝑲𝒈 𝒎𝒐𝒍
𝑹𝑻 𝟑𝟎𝟎𝑲 𝟖. 𝟑𝟏𝟒 𝒌𝒑𝒂 . 𝒎𝟑
Path A (the constant pressure process):
𝒗𝟐 𝒗𝟐
𝑾=− 𝒑 𝒅𝑽 = − 𝒑 𝑽𝟐 − 𝑽𝟏 = − 𝟐𝟎𝟎 × 𝟏𝟎𝟑 𝒑𝒂 𝟎. 𝟏 𝒎𝟑 = −𝟐𝟎 𝒌𝑱
𝒗𝟏 𝒗𝟏
Path B (the constant temperature process):
𝒗𝟐 𝒏𝑹𝑻 𝑽
𝑾= 𝒗𝟏 𝑽
𝒅𝑽 = − 𝒏𝑹𝑻 𝒍𝒏 ( 𝟐) = −(𝟎. 𝟎𝟎𝟖𝟎𝟐)(𝟖. 𝟑𝟏𝟒)(𝟑𝟎𝟎𝑲) 𝒍𝒏 (𝟐)=-13.86 kJ
𝑽𝟏
Electrical work: Electrical work occurs when an electrical current passes through an
electrical resistance in the circuit. If the system generates an electrical current (e.g., an
electrical generator
inside the system) and the current passes through an electrical resistance outside the system, the
electrical work is negative because the electrical work is done on the surroundings.
Shaft work: Shaft work occurs when the system causes a shaft
to turn against an external mechanical resistance.
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9.2. Types of Energy to Be Included in Energy Balances
Flow work: Flow work is performed on the system when a fluid is pushed into the system by
the surroundings..
Flow in Flow out
9.2.3. Kinetic Energy (KE)
`is the energy a system, or some material, possesses because of its velocity relative to the
surroundings, which are usually, but not always, at rest. The wind, moving automobiles,
waterfalls, flowing fluids, and so on possess kinetic energy.
𝟏
𝑲𝑬 = 𝒎𝑽𝟐
𝟐
Example 9.3: Water is pumped from a storage tank through a tube of 3.00 cm inner diameter at
the rate of 0.001 m3/s. What is the specific kinetic energy of the water in the tube?
𝑸 𝟎. 𝟎𝟎𝟏
𝑽= = = 𝟏. 𝟒𝟏𝟓 𝒎/𝒔
𝑨 𝝅 (𝟎. 𝟎𝟏𝟓)𝟐
𝟏
𝑲𝑬 = 𝟎. 𝟎𝟎𝟏 𝟏. 𝟒𝟏𝟓 = 𝟎. 𝟎𝟎𝟎𝟕𝟏 𝐉
𝟐
9.2. Types of Energy to Be Included in Energy Balances
9.2.4. Potential Energy (PE)
• Potential energy (PE) is energy a system possesses because of the force exerted on its mass by a
gravitational or electromagnetic field with respect to a reference surface.
𝑷𝑬 = 𝒎𝒈𝒉
Example 9.4.: Water is pumped from one reservoir to another 300 ft away, as shown in Figure
E9.4. The water level in the second reservoir is 40 ft above the water level of the first reservoir.
What is the increase in specific potential energy of the water in British thermal units per pound
(mass)?
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9.2. Types of Energy to Be Included in Energy Balances
9.2.5. Internal energy (U) is a macroscopic concept that takes into account the molecular,
atomic, and subatomic energies of entities, all of which follow definite microscopic conservation
rules for dynamic systems. Specific internal energy is a state variable and can be stored.
𝑼𝟐 𝑻𝟐
∆𝑼 = 𝑼 𝟐 − 𝑼 𝟏 = 𝒅𝑼 = 𝑪𝒑 𝒅𝑻
𝑼𝟏 𝑻𝟏
Example 9.5: What is the change in internal energy when 10 kg mol of air are cooled from 60°C
to 30°C in a constant volume process?
𝑻𝟐 𝟑𝟎
∆𝑼 = 𝒎 𝑪𝒑 𝒅𝑻 = 𝟏𝟎 𝟐. 𝟏 × 𝟏𝟎𝟒 𝒅𝑻 = 𝟐. 𝟏 × 𝟏𝟎𝟓 𝟑𝟎 − 𝟔𝟎 = −𝟔. 𝟑 𝟏𝟎𝟔 𝑱
𝑻𝟏 𝟔𝟎
9.2.6. Enthalpy
You will find later in this chapter that the
two terms (U + pV) and (Û + p ) do not
appear in an energy balance.
𝑻𝟐
∆𝑯 = 𝒎 𝑪𝒑 𝒅𝑻
𝑻𝟏 Figure 9.11. The overall enthalpy change includes the
sensible heats (the enthalpy changes within a phase) plus the
latent heats (the enthalpy changes of the phase transitions).
9.2. Types of Energy to Be Included in Energy Balances
Example 9.6: Calculate the enthalpy change for the process in Example 9.5, except assume that
the enthalpy change occurs in a constant pressure process.
𝑻𝟐 𝟑𝟎
∆𝑯 = 𝒎 𝑪𝒗 𝒅𝑻 = 𝟏𝟎 𝟐. 𝟗 × 𝟏𝟎𝟒 𝒅𝑻 = 𝟐. 𝟏 × 𝟏𝟎𝟓 𝟑𝟎 − 𝟔𝟎 = −𝟖. 𝟕 × 𝟏𝟎𝟔 𝑱
𝑻𝟏 𝟔𝟎
9.2.7. Heat Capacity
Quite a few sources exist for equations expressing Cp as a function of T, and numerous charts
exist on which Cp is plotted as a function of temperature.
𝑪𝒑 = 𝒂 + 𝒃𝑻 + 𝒄𝑻𝟐 + 𝒅 𝑻𝟑
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9.2. Types of Energy to Be Included in Energy Balances
9.2.8. Enthalpies for Phase Transitions
• Relations to estimate values for ΔHv
1. Chen’s equation
𝑻𝒃
𝟑. 𝟗𝟕𝟓 − 𝟑. 𝟗𝟖𝟑 + 𝟏. 𝟓𝟓𝟓𝒍𝒏𝒑𝒄
∆𝑯𝒗 = 𝑹𝑻𝒃 𝑻𝒄
𝑻𝒃
𝟏. 𝟎𝟕 − ( )
𝑻𝒄
where Tb is the normal boiling point of the liquid in kelvin, Tc is the critical temperature in kelvin,
and pc is the critical pressure in atmospheres.
2. Riedel’s equation
𝑻𝒃(𝒍𝒏 𝒑𝒄−𝟏)
∆𝑯𝒄 = 𝟏. 𝟎𝟗𝟑 𝑹𝑻𝒄 𝑻𝒃
𝑻𝒄(𝟎.𝟗𝟑𝟎−( )
𝑻𝒄
3. Watson’s equation
𝟎.𝟑𝟖
∆𝑯𝒗 𝟏 − 𝑻𝒓𝟐 Where
=
∆𝑯𝒗 𝟏 − 𝑻𝒓𝟏 ΔHv1 = heat of vaporization of a pure liquid at T1
ΔHv1 = heat of vaporization of the same liquid at T2
9.2. Types of Energy to Be Included in Energy Balances
Example 9.8: Use Chen’s equation to estimate the heat of vaporization of acetone at its normal
boiling point, and compare your results with the experimental value of 30.2 kJ/g mol listed in
Appendix F.
The basis is 1 g mol.
Normal boiling point: 329.2 K
Tc: 508.0 K
pc: 47.0 atm
Chen’s equation
𝑻𝒃
𝟑. 𝟗𝟕𝟓 − 𝟑. 𝟗𝟖𝟑 + 𝟏. 𝟓𝟓𝟓𝒍𝒏𝒑𝒄
∆𝑯𝒗 = 𝑹𝑻𝒃 𝑻𝒄
𝑻𝒃
𝟏. 𝟎𝟕 − ( )
𝑻𝒄
𝟑𝟐𝟗. 𝟐
𝟑. 𝟗𝟕𝟓 − 𝟑. 𝟗𝟖𝟑 + 𝟏. 𝟓𝟓𝟓 𝒍𝒏(𝟒𝟕) 𝒌𝑱
∆𝑯𝒗 = 𝟖. 𝟑𝟏𝟒 (𝟑𝟐𝟗. 𝟐) 𝟓𝟎𝟖 = 𝟑𝟎
𝟑𝟐𝟗. 𝟐 𝒈𝒎𝒐𝒍
𝟏. 𝟎𝟕 − ( )
𝟓𝟎𝟖
(𝒊𝒏𝒔𝒊𝒈𝒏𝒊𝒇𝒊𝒄𝒂𝒏𝒕 𝒆𝒓𝒓𝒐𝒓)
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9.3 Energy Balances without Reaction
9.2.9. Tables and Charts to Retrieve Enthalpy Values
Figure 9.13. At higher pressures in which the compound is liquid, the lines of constant temperature (such as
600°F) are almost vertical, and thus the enthalpy of the saturated liquid can be substituted for the actual
enthalpy if necessary.
9.3 Energy Balances without Reaction
Figure 9.14. A pressure-versus-enthalpy chart for butane showing lines of constant temperature and constant
specific volume
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9.3 Energy Balances without Reaction
Ex. Calculate ΔĤ, Δ , and ΔT
for 1 lb of saturated vapor of
n-butane going from 2 atm to
20 atm (saturated).