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화공열역학 I (Chemical Engineering Thermodynamics I)

Introduction
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The Scope of Thermodynamics

Terminology

‘Thermodynamics’: Thermo + Dynamics

Related to Energy, Heat Transfer, and Equilibrium.

System & Surrounding

The application of thermodynamics to any real problem starts with the identification of a particular body of
matter as the focus of attention.

Surrounding
System

The thermodynamic state of the system is defined by a few measurable macroscopic properties.
e.g., length, time, mass, temperature, and amount of substance.
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Dimensions and Units

Dimensions

Mass (𝑚), Length (𝑙), Time (𝑡)

Units

The primary units of measurement are set by international agreement and codified as the International
System of Units (abbreviated SI, for Le Système International d'Unités)

The base unit of time is the second, s

The base unit of length is the meter, m
The base unit of mass is the kilogram, kg
The temperature unit is the Kelvin, K
The unit defining the amount of material is the mole, mol

‘MKS unit’ : Meter, Kilogram, Second

‘CGS unit’ : Centimeter, Gram, Second
‘English engineering unit – FPS unit’ : Feet, Pound, Second
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Measures of Amount or Size

Three common measures of amount or size

Mass (𝑚), Number of moles (𝑛), Total volume (𝑉 𝒕 )

𝑚
Molar mass, 𝑀 = 𝑛

𝑉𝒕
Specific volume, 𝑉 ≡ [cm3 Τkg]
𝑚

𝑉𝒕
Molar volume, 𝑉 ≡ [cm3 Τmol]
𝑛

Specific or molar density is defined as the reciprocal of specific or molar volume: 𝜌 ≡ 𝑉 −1

These quantities (specific/molar volume and specific/molar density) are independent of the size of a system,
and are examples of intensive thermodynamic variables.

Intensive property (or variable): 𝑇, 𝑃, 𝑉, 𝑈, 𝑆, 𝐺

Extensive property (or variable): 𝑉 𝒕 , 𝑈 𝒕 , 𝑆 𝒕 , 𝐺 𝒕
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Force

Force & Power

Force ( ) [N]
Power ( ) W = [JΤS]

Newton’s second law: 𝐹 = 𝑚𝑎

1 N = 1 kg ∙ m ∙ s −2

Mass ( ) 6 kg
Weight ( )

cf) 1 pound force (lbf ) & 1 pound mass (lbm )

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Temperature

Celsius scale, Kelvin scale / Fahrenheit scale, Rankine scale

The ice point (freezing point of water saturated with air at standard atmospheric pressure)
Celsius scale: 0 ℃ Fahrenheit scale: 32 ℉
Kelvin: 273.15 K Rankine: 491.67 R → “Absolute temperature” (w/o °)

𝑡 ℉ = 1.8 𝑡 ℃ + 32

𝑇 K = 𝑡 ℃ + 273.15 𝑇 R = 𝑡 ℉ + 459.67

𝑇 R = 1.8 𝑇 K

The Celsius degree and the kelvin represent

the same temperature interval,
as do the Fahrenheit degree and the rankine.
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Pressure

Pressure

The pressure 𝑷 exerted by a fluid on a surface is defined as the ‘normal’ force exerted by the fluid per ‘unit

𝐹
area’ of the surface. 𝑷=𝐴
If force is measured in N and area in m2 , the unit is the newton per square meter or Nm−2 , called the pascal
(Pa), the basic SI unit of pressure.

cf) In the English engineering system, a common unit is the pound force per square inch (psi), lbf /in2

1 bar = 105 Pa = 0.986923 atm = 14.5038 psi

Most pressure gauges give readings which are the difference between the pressure of interest and the
pressure of the surrounding atmosphere. These readings are known as gauge pressures, and can be
converted to absolute pressures by addition of the barometric pressure.

Absolute pressure = Gauge pressure + Atmospheric pressure

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Pressure

Example

A dead-weight gauge with a 1- cm -diameter piston is used to measure pressures very accurately. In a particular instance, a
mass of 6.14 kg (including piston and pan) brings it into balance. If the local acceleration of gravity is 9.82 ms −2 , what is the
gauge pressure being measured? If the barometric pressure is 748 torr, what is the absolute pressure?

Dead-weight gauge
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Work

Work

Work 𝑊 is performed whenever a force acts through a distance. By definition, the quantity of work is given
by the equation: 𝑑𝑊 = 𝐹 𝑑𝑙 where 𝐹 is the component of force acting along the line of the displacement 𝑑𝑙.
𝐹 =𝑃∙𝐴 𝑉𝑡
𝑑𝑊 = 𝑃 ∙ 𝐴 ∙ 𝑑 = 𝑃 ∙ 𝑑𝑉 𝑡
𝑡
𝑑𝑙 = 𝑑(𝑉 ൗ𝐴) 𝐴

(𝐴: cross-sectional area, constant)

By the way, work is regarded as positive when the displacement is in the same direction as the applied force
and negative when they are in opposite directions.

𝑉𝑡
∴ 𝑑𝑊 = − 𝑃 ∙ 𝑑𝑉 𝑡 , 𝑊 = − ‫𝑡 𝑉׬‬2 𝑃 ∙ 𝑑𝑉 𝑡
1
The minus signs in these equations are made necessary by
𝑃 𝑃 the sign convention adopted for work.
When the piston moves into the cylinder so as to compress

∆𝑙
the fluid, the applied force and its displacement are in the
𝑙1
same direction; the work is therefore positive.
𝑙2 ∆𝑙

𝑉1𝑡 𝑉2𝑡
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Work

Work – PV diagram
𝑃1 𝑃2
From point 1 to point 2: Compression
From point 2 to point 1: Expansion
∆𝑙
𝑙1
𝑙2 ∆𝑙
𝑉2𝑡

𝑉1𝑡 𝑉2𝑡
𝑊 = − න 𝑃 ∙ 𝑑𝑉 𝑡 → The area under the curve
𝑉1𝑡
= work done by compression (+)

𝑉1𝑡
𝑊 = − න 𝑃 ∙ 𝑑𝑉 𝑡 → The area under the curve
𝑉2𝑡
= work done by expansion (-)

The SI unit of work: J (Joule)

1J=1N∙m
cf) In the English engineering system, the unit often used is
the foot-pound force (ft lbf )
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Energy

Types of Energy

1) Kinetic Energy

When a body of mass 𝑚, acted upon by a force 𝐹, is displaced a distance 𝑑𝑙 during a differential interval of
time 𝑑𝑡, the work done is given by 𝑑𝑊 = 𝐹 𝑑𝑙. In combination with Newton’s second law, 𝑑𝑊 = 𝑚𝑎 𝑑𝑙.

By definition, the acceleration is 𝑎 = 𝑑𝑢/𝑑𝑡, where 𝑢 is the velocity of the body. Thus,
𝑑𝑢 𝑑𝑙
𝑑𝑊 = 𝑚𝑎 𝑑𝑙 = 𝑚 𝑑𝑙 = 𝑚 𝑑𝑢 = 𝑚𝑢 𝑑𝑢
𝑑𝑡 𝑑𝑡

The integration with a finite change in velocity from 𝑢1 to 𝑢2 ,

𝑢2
𝑢22 𝑢12 𝑚𝑢22 𝑚𝑢12 𝑚𝑢2
𝑊 = 𝑚 න 𝑢 𝑑𝑢 = 𝑚 − = − = ∆( )
𝑢1 2 2 2 2 2

1
𝐸𝐾 = 𝑚𝑢2
2
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Energy

Types of Energy

2) Potential Energy

If a body of mass 𝑚 is raised from an initial elevation 𝑧1 to a final elevation 𝑧2 , an upward force at least
equal to the weight of the body must be exerted on it, and this force must move through the distance 𝑧2 − 𝑧1 .
Because the weight of the body is the force of gravity on it, the minimum force required is given by Newton’s
law: 𝐹 = 𝑚𝑎 = 𝑚𝑔, where 𝑔 is the local acceleration of gravity.

The minimum work required to raise the body is the product of this force and the change in elevation:
𝑊 = 𝐹 𝑧2 − 𝑧1 = 𝑚𝑔 𝑧2 − 𝑧1 = 𝑚𝑔𝑧2 − 𝑚𝑔𝑧1 = ∆(𝑚𝑔𝑧)
𝐸𝑃 = 𝑚𝑔𝑧

Conservation of Energy

∆𝐸𝐾 + ∆𝐸𝑃 = 0
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Heat

Heat

A hot object brought in contact with a cold object becomes cooler, whereas the cold object becomes warmer.
A reasonable view is that something is transferred from the hot object to the cold one, and we call that
something heat, 𝑄.

Heat always flows (naturally) from a higher temperature to a lower one, leading to the concept of temperature
as a driving force for heat transfer.

Heat, 𝑄, has the same units as work and energy, joule.

1 J = 1 N ∙ m = 0.239 cal = 9.47831 × 10−4 Btu (British thermal unit)

1 cal: the amount of thermal energy needed to increase the temperature of 1 gram of water by 1 ℃.