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THERMODYNAMICS I

Introduction and Basic Concepts of Chemical Engineering

Thermodynamics
Department of Chemical Engineering, Semarang State University
Dhoni Hartanto S.T., M.T., M.Sc.
 Course Details
Course title : Thermodynamics 1
Time slot : Monday, 11.00 – 13.00 am
Classroom/credit : E2-307/ 2 sks
Instructor : Dhoni Hartanto, S.T., M.T., M.Sc.
Office : E-2 building, Faculty of engineering, UNNES
Telephone : +62821-4154-8851
E-mail : dhoni.hartanto@gmail.com
Office hours : Monday-Friday 07.00 am– 04.00 pm

Course books : Smith, J. M., Van Ness, H.C., Abbott, M. M. 2011. Introduction to
Chemical Engineering Thermodynamics, 6th ed., McGraw-Hill
Co., Singapore.
References books :
1. Poling, B. E., Prausnitz, J. M., O’Connell. 2001. The properties of gases and liquids
fifth edition, McGraw-Hill, New York, USA.
2. Sandler, S. I. 1999, Chemical Chemical, Biochemical, and Engineering
Thermodynamics, 5th ed., Joh Wiley and Sons, Inc., USA
3. Praustnitz, J. M., Lichtenthaler, R. N., and de Azevedo, E. G. 1999. Molecular
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Thermodynamics of Fluid-Phase Equilibria, 3rd ed., Prentice Hall PTR. USA.
 Course Details (cont.)

Ref. Book : Poling, 2001

Ref. Book : Praustnitz, 1999

Course book : Smith, 2011
Ref. Book : Sandler, 1999

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 Topics

1. Thermodynamics : Definition
2. Thermodynamics : Example
3. Dimensions and Units
4. Measures of Amount or Size
5. Force
6. Temperature
7. Pressure
8. Work
9. Energy
10. Heat

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 Definition

Thermodynamics: The science of energy

The name thermodynamics stems from the Greek words therme (heat)
and dynamics (motion)

Thermodynamics is the study of energy conversion between heat and

mechanical work, and subsequently the macroscopic variables such as
temperature, volume, and pressure.

THERMO : HEAT and TEMPERATURE

DYNAMICS : MOTION

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 Introduction
KEYWORDS:

CHEMICAL INOVATIVE PRODUCTS

DIPPR
ENGINEERS
ECONOMIC EVALUATIONS
GREEN TECHNOLOGY
CONCEPTUAL DESIGN

BASIC DESIGN
DECHEMA PROCESS SIMULATION

PILOT PLANT SOLUTIONS

THERMODYNAMICS
SCALE UP
ENVIRONMENT EXPERIMENT
NCBI GREEN CHEMICAL
OPTIMAZION NIST
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 The importance of
thermodynamics

NIST, DIPPR, DECHEMA, Journal

P T

Q, W, Equilibrium conditions
Published Measurements
Data
(online or printed)

Thermodynamic
Properties :
• Activity coefficient
(Wilson, NRTL,
UNIQUAC, UNIFAC,
COSMO-RS, Physical & Chemical Processes
COSMO-SAC)
• EoS: virial, vdW, RK, Simulation process i.e using ASPEN
SRK, PR, Gen.
Corrr.) 30% effort used in physical properties
(Chen and Mathias, AIChE, 48 (2002) 194-
200)
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 Thermodynamics Systematics

Abstract World
Abstract Solution
Abstract Problem

Real PROBLEM Real Solution

Real World

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 Example

The production of chemicals, polymers, pharmaceuticals and other

biological materials, and oil and gas processing, all involve chemical or
biochemical reaction that produce a mixture of reaction product.

(e.g : production of tert-butanol)

1. These must be separated from the mixture and purified to result in

product of societal, commercial, or medicinal value.
2. These is the area where thermodynamics plays a central role in
process eng.
3. Separation processes, e.g. distillation are designed based on
information from thermodynamics such as vapor-liquid equilibrium
data.

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 Example (cont.)

Vapor-Liquid
Equilibrium
(VLE) data

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 Example (cont.)

Feed Extractive
Distillation Column
Preheater

Steam in

Concentrated
Evaporator
Buffer Solution

Condense out

Pump

Distillation method based on the addition
of an entrainer (extractive distillation)
(Hartanto, D. et al, 2013)
Buffering-effect of TRIS on the VLE of the tert-butanol (1) +
water (2) system. x1' was calculated from buffer-free base :
(■), 0.05; (▲), 0.10; (●), 0.20; (___), calculated from the
NRTL-HOC model; (-∙∙-), smoothed results for the TRIS-free
system (Hartanto, D. et al 2016)
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 Dimensions
and Units
- Dimension is recognize through our sensory perceptions and not
definable without the definition of arbitrary scales of measure,
divided into specific units of size.

The units have been set by international

agreement, and are
codified as the International System of Units (SI).

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 Dimensions
and Units (cont.)
 Any physical quantity can be characterized by
dimensions.
 The magnitudes assigned to the dimensions are
called units.
 Some basic dimensions such as mass m, length L,
time t, and temperature T are selected as primary or
fundamental dimensions, while others such as
velocity V, energy E, and volume V are expressed in
terms of the primary dimensions and are called
secondary dimensions, or derived dimensions.
 Metric SI system: A simple and logical system based
on a decimal relationship between the various units.
 English system: It has no apparent systematic
numerical base, and various units in this system are
related to each other rather arbitrarily.

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 Dimensions
and Units (cont.)
Dimensions and Units in HYSYS v8.4

SI units American Engineering Units

(Field)

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 Dimensions and
Units (cont.)
Dimensional Homogeneity
Unity Conversion Ratios
All nonprimary units (secondary units) can be formed by
combinations of primary units.
Force units, for example, can be expressed as

They can also be expressed more conveniently

as unity conversion ratios as

Unity conversion ratios are identically equal to 1 and are

unitless, and thus such ratios (or their inverses) can be
inserted conveniently into any calculation to properly
convert units.
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 Measurements
of Amount and Size
•Three measures of amount or size are in common use:
Mass, m ; Number of moles, n ; Total volume, Vt

• Mass, m divided by the molar mass M (molecular weight) to yield

number of moles;

m
n , m  Mn
M
Total volume, divided by the mass or number of moles of the
system to yield specific or molar volume.

• Specific volume: Vt V t  mV
V or
m

Vt
• Molar Volume: V or V t  nV
n
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 Measurements of
Amount and Size (cont.)

Properties in HYSYS

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 Force

SI unit Metric engineering

system units
Newton (N) Kilogram force (kgf)
1
F  ma
F = ma gc

1
1 kgf  x 1 kg x 9.80665 ms  2
gc
gc  9 .80665 kg m kg f 1 s  2

* Note : The kilogram force is equivalent to 9.80665 N

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 Temperature
 All temperature scales are based on some easily reproducible states such as the
freezing and boiling points of water: the ice point and the steam point.
 Ice point: A mixture of ice and water that is in equilibrium with air saturated with
vapor at 1 atm pressure (0°C or 32°F).
 Steam point: A mixture of liquid water and water vapor (with no air) in equilibrium
at 1 atm pressure (100°C or 212°F).
 Celsius scale: in SI unit system
 Fahrenheit scale: in English unit system
 Thermodynamic temperature scale: A temperature scale that is independent of the
properties of any substance.
 Kelvin scale (SI) Rankine scale (E)
 A temperature scale nearly identical to the Kelvin scale is the ideal-gas temperature
scale. The temperatures on this scale are measured using a constant-volume gas
thermometer.

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Temperature (cont.)

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 Pressure
Pressure: A normal force exerted by a fluid per unit area
F mg
P 
A A
F mg Ahg
P    hg
A A A

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 Pressure (cont.)
Absolute pressure: The actual pressure at a given position. It is measured
relative to absolute vacuum (i.e., absolute zero pressure).
Gage pressure: The difference between the absolute pressure and the local
atmospheric pressure. Most pressure-measuring devices are calibrated to read
zero in the atmosphere, and so they indicate gage pressure.
Vacuum pressures: Pressures below atmospheric pressure

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Energy

Work (W)
Heat (Q)
Kinetic Energy (Ek)
Potential Energy (Ep)
Internal Energy (U)

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 Work (W)
dW  Fdl
Kerja diikuti oleh perubahan volume dari fluida (ex. Compression of a
gas by a piston)
V t 
dW   PAd  
 A 
V2t
W    t PdV t Total volume gives total work
V1
V2
W    PdV Work per unit mass or mole
V1

Tanda negatif menunjukkan bahwa kompresi

W+ fluida didifinisikan sebagai kerja positif

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Heat (Q)
Q  heat

-Heat moves from object with higher T to object with lower T

-Temperature difference is driving force of heat flow

W & Q are path variables

• Path variables only have meaning when exchange

between a system/substance and surroundings
• A substance does not contain a certain amount of work or
heat

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Kinetic Energy(Ek)
1
E K  mu 2
2
Potential Energy(Ep)
Ep  mgz

Internal Energy(U)
U  internal energy due to intermolecular forces
We will focus on 5 forms of energy

Question:
what is the relationship between the various forms of
energy?
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 First Law

Total energy is constant

-DE(environment)
DE(system)
Q＋ W+
DEk, DEp,
DU

DE(system) + DE(environment) = 0

DU  DEk  DEp sistem  Q  W  0

DU  DEk  DEP  Q  W First law formulation
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Thank you

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