CHE 203:

CHEMICAL ENGINEERING THERMODYNAMICS

THE FIRST LAW OF THERMODYNAMICS

APPLIED ON CLOSED SYSTEM

Engr. Michael Allan Ramos, M.Sc. M.Eng.Sc.

Assistant Professor, Chemical Engineering Department
College of Engineering and Architecture
Technological Institute of the Philippines – Manila

2nd Semester, A.Y. 2019 - 2020

Internal Energy, U
• Refers to energy of the molecules comprising the substance (i.e.
energies of translation, rotation, and vibration)

• Includes potential energy associated with intermolecular forces

(i.e. attractive/repulsive forces)

• Includes the energy of chemical bonds that hold atoms together

as molecules (i.e. interaction of electrons and nuclei of atoms)

• Is a thermodynamic primitive, cannot be directly measured, and

absolute values are unknown
The System and its Surroundings
System
• represents the region of interest;
• can be a specific object or location;
• May be of any size;
• its boundaries may be real or
imaginary, rigid or flexible.
Surroundings
• everything with which the system interacts
Types of Thermodynamic System

Matter
OPEN CLOSED ISOLATED
SYSTEM SYSTEM SYSTEM
Energy
First Law of Thermodynamics

Δ 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 + Δ 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = 0

• Potential
Energy quantities associated with a system;
• Kinetic
reside with and are stored with matter
• Internal
Energy
• Heat Energy flows in transit across the boundary;
• Work Never store or contained in a system
Energy Balance for Closed Systems
• System whose mass is necessarily constant
• No energy associated with matter is transported across the
boundary
• All energy exchange with its surroundings is in the form of heat
and work
𝜟 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒚𝒔𝒕𝒆𝒎 = 𝑸 + 𝑾
Sign Convention Positive (+): surroundings à system
Negative (-): system à surroundings

By the surroundings/system +/-

From the surroundings/system +/-
To the surroundings/system -/+
Energy Balance for Closed Systems

Finite changes in internal energy: Differential changes in internal energy:

𝜟 𝑼𝒕 = 𝑸 + 𝑾 𝒅𝑼𝒕 = 𝒅𝑸 + 𝒅𝑾
𝜟 𝒏𝑼 = 𝒏 ∆𝑼 = 𝑸 + 𝑾 𝒅 𝒏𝑼 = 𝒏 𝒅𝑼 = 𝒅𝑸 + 𝒅𝑾
Equilibrium and Thermodynamic State
• Absence of change and of any tendency toward change on a
macroscopic level
• All forces are in exact balance resulting to a static condition

Reflect changes in Account for the energy

thermodynamic state of the 𝒏 ∆𝑼 = 𝑸 + 𝑾 changes that occur in the
system as reflected by its surroundings
properties (P, V, T) Path Functions
State Functions (Process-dependent)
(Independent of process)
Illustrative Calculations
Reversible Process

• Ideal process that produces a best possible result (i.e. minimum

work input required or maximum work output attainable)

• Sets a limit to the performance of an actual processes

Summary Remarks on Reversible Processes
• Can be reversed at any point by an
infinitesimal change in external conditions
• Is never more than minutely removed from
equilibrium
• Traverses a succession of equilibrium states
• Is frictionless
• Is driven by forces whose imbalance is
infinitesimal in magnitude
• Proceeds infinitely slowly
• When reversed, retraces its path, restoring
the initial state of system and surroundings
Summary Remarks on Reversible Processes
Illustrative Calculations
Closed-System Reversible Processes
For convenient calculation of changes in state functions for a specific
change of state:

𝒅𝑼 = 𝒅𝑸
Constant-Volume change of state
𝚫𝑼 = 𝑸

𝒅𝑯 = 𝒅𝑸
Constant-Pressure change of state
𝚫𝑯 = 𝑸 Where H = Enthalpy = U + PV (also a state function)
𝛥𝐻 = ∆𝑈 + ∆(𝑃𝑉)
Heat Capacity, C
• Denotes the amount of heat needed to raise the temperature of a specific
substance by one degree.
𝒅𝑸
𝑪≡
𝒅𝑻
• Process-dependent quantity or a path function

𝝏𝑼 𝑻𝟐
Mechanically reversible 𝑪𝑽 ≡ 𝑸 = ∆𝑼 = T 𝑪𝑽 𝒅𝑻
constant-volume process: 𝝏𝑻 𝑽 𝑻𝟏

𝝏𝑯 𝑻𝟐
Mechanically reversible
𝑪𝑷 ≡ 𝑸 = ∆𝑯 = T 𝑪𝑷 𝒅𝑻
constant-pressure process: 𝝏𝑻 𝑷 𝑻𝟏
State Functions as Process-Independent
Illustrative Calculations
END.