Fundamental

Thermodynamic
Chemical Engineering Tools
• Mass Balance
• Energy Balance
Thermodynamic
• Equillibrium
• Rate processes
• Economy
• Humanity
Reference:
1. Prausnitz, “Molecular Thermodynamic”
-) Main reference for first-half of the semester
-) Good explanation in fundamental definition
2. Smith & Van Ness, “Introduction to Chemical Engineering Thermodynamic”
-) Main reference for second-half of the semester
-) Provides theory and application in chemical industry
-) Provides important thermodynamic data (Cp, steam table, dHf, dG, dS, etc)
 Subjects of the Fundamental
Thermodynamic (First-Half of The Semester)
• Overview of basic concepts (1st & 2nd law of thermodynamic)
-) Entalpy (H), Work (W), Heat (Q), flow process, non-flow process, entropy(S), Gibbs-free energy (G)
• Maxwell correlation for state function
-) State Function (Ideal gas & real gas)
-) Hypothetical path (isobaric, isothermic, isochoric, phase-changing, phase equillibrium)
-) How to utilize Maxwell correlation
• Phase equilibrium for pure components
-) Fugacity concept
-) for real gas
-) includes Maxwell correlation subjects
• Phase equilibrium for multi-components
-) fugacity & activity concept
-) assumptions to simplify calculation
Notes: Most-used terminology
• Pressure
-) P: total pressure of the system (summation of each component’s partial pressure in the system)
-) P0/Psat : Vapor pressure (pressure which developed by each liquid component in the system 
when vapor pressure = total pressure, the liquid starts to turn into gas phase/boiling)
-) p: partial pressure (pressure which developed by each gas component in the system)

• Calculation of partial pressure:

pi = yi P (Dalton’s law)
pi = xi P0 (Raoult’s law)
x = mole fraction (for liquid phase); y= mole fraction (for gas phase)
mole fraction = mole of certain component/ total mole in the system

• Enthalpy (H): Energy which contained by substance/material (flow/non-flow)

• Heat (Q): Form of energy which transferred from system to surrounding, without material flow
• Equation of State (EOS): Equation which relates P,V and T of substances, mainly in gas phase
-) Ideal Gas: Pv=RT (only valid for low pressure; v=volume/mole; V=volume)
-) Van der Waals, Virial, Redlich-Kwong, etc.
Type of the problems
1.Define condition in state-2 (P2, T2, etc..) with known-condition is state-1
(P1, T1,etc.,.)  can be exact value or equation
2.Calculate how much condensate/vapor is formed during process
3.Calculate W, Q, enthalpy change, etc.
4.Define condition in state-2 (P2, T2, etc..) for phase equilibrium system with
known-condition is state-1 (P1, T1,etc.,.)  can be exact value or equation

IDEAL/NON-IDEAL SYSTEM, HYPOTHETICAL PATH, EQUATION OF

STATE
Termodinamika
• Mempelajari interaksi zat dengan energi

Total QUANTITY energy of the SYSTEM and ITS

SURROUNDING is CONSTANT.

Boundary (can be
SYSTEM real or imaginary;
rigid or flexible)
surroundings
Termodinamika
Two types of exchange can occur between the system and the
surrounding :
a) Energy exchange : heat, work, friction, radiation, etc.
b) Matter (mass) exchange : movement of molecules
(mass) across the boundary.

Based on the type of exchange, there are 3 types of system :

a) Isolated system : no exchange of matter or energy
b) Closed system : no exchange of matter; some
exchange of energy
c) Open system : exchange of both matter and energy
 State
"State" refers to temperature, pressure and the amount and type of
substance present in the system/surrounding

State-1: P1, T1, State-2: P2, T1,

constant mol constant mol

State/State variable
merujuk pada besaran
“intrinsic”

State-3: P1, T2,

constant mol
 Equation of State
Equation to correlate a parameter to other parameter, in a state

P= known

V= known How much is the amount

of gas inside (in mol)

T= known

𝑃V = n𝑅𝑇
 Equation of State
Ideal Gas Non-Ideal Gas (Real Gas)
1. Usually used if system has low Usually used for high pressure
pressure
1. For all gases (independent of gas certain equation only can be used for certain
types) type of gas
1. Can be used for calculation, if In question, if we are asked to calculate using
question does not mention process non-ideal question, the question usually
condition/EoS which should be used provides the non-ideal gas equation.

Note: Untuk pengerjaan soal, jangan lupa Note: Untuk pengerjaan soal, soal yang
dituliskan bahwa sistem diasumsi dapat meminta kita mengerjakan dengan non-ideal,
didekati dengan gas ideal. biasanya sudah menuliskan persamaannya

𝑃𝑣 = 𝑅𝑇 Van der Waals:

𝑅𝑇 𝑎
𝑃= − 2
𝑣−𝑏 𝑣

Virial:
𝐵𝑃
𝑃𝑣 = 1 +
𝑅𝑇

Note: the value of a,b and B depend on gas

type
 State Function
Parameter/value of a system which only influenced by initial state and
final state (Enthalpy, Entropy, Gibbs Free Energy, Internal Energy, etc..)

State-2: P2, T2,

State-1: P1, T1, ΔH2=200 kJ/mol
ΔH1=150 kJ/mol

ΔH12=50 kJ/mol

Maxwell Equation &

How we calculate state function? Equation of State
 Hypothetical Path
Imaginary/hypothetical process/path that we develop to describe
the change of state of a system
Hypothetical Path:
State-1: P1, T1 State-2: P2, T2 1
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 2
𝐼𝑠𝑜𝑏𝑎𝑟𝑖𝑐

P1, T1 P2, T1 P2, T2

1 2
𝐼𝑠𝑜𝑏𝑎𝑟𝑖𝑐 𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙

P1, T1 P2, T1 P2, T2

1 𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝐼𝑠𝑜𝑏𝑎𝑟𝑖𝑐 𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙

P2, T2
P1, T1 P ≈ 0, T1 P ≈ 0, T2
1. Ethane is expanded through turbine which operates isothermally reversible at T=278 K. The initial pressure of
ethane is 15 atm and the final pressure is 5 atm.
a) Calculate work done by turbine (per mol of ethane)
b) Calculate heat absorbed by turbine (per mol of ethane)
c) Calculate entopy change (per mol of ethane)

It is known that ethane follows EoS as follows:

𝑃𝑣 𝐵𝑃 𝑑𝐵
= 1 + 𝑅𝑇 , at T=278 K, B=-217.9 cm3/mol and 𝑑𝑇 = 1.455 cm3/mol
𝑅𝑇
Heat capacity at ideal condition (Cp0)=12.60 cal/mol.K
(Quiz, January 23, 2014)

2. Binary mixture of liquid Chloroform (1) and Ethanol (2) at 550C follows Margules Eq. below:
𝑔𝐸
= (1,42𝑥1 + 0,59𝑥2 )𝑥1 𝑥2
𝑅𝑇
At 550C, Chloroform and Ethanol have vapor pressure of 82,37 kPa and 37,31 kPa respectively. It is assumed
that the mixture of vapor formed follows ideal gas. If at that temperature, the composition of the liquid is
50% Chloroform and 50% ethanol, evaluate whether that mixture can formed azeotrope or not! (Modified
from Final Exam, 4th June 2018)
3. Gas follows equation of state below:
𝑃𝑣 𝐵𝑃 𝑏
= 1 + 𝑅𝑇 ; with 𝐵 = 𝑎 − 𝑇; a and b are constant
𝑅𝑇
Heat capacity at constant pressure is Cp0. Initially, the gas which has condition of T1,P1 is then
expanded isothermally into P2. Derive the equation to calculate outlet temperature.
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