Introduction to Chemical

Engineering
Teaching by:
Vassily Hatzimanikatis (vassily.hatzimanikatis@epfl.ch)

Assistants:
Denis Joly (denis.joly@epfl.ch)
Konrad Lagoda (konrad.lagoda@epfl.ch)
Zi Xuan Ng (zixuan.ng@epfl.ch)

Office hours: Mondays 16h-19h (CH H4 625) or schedule by email

Fridays, 14h15 - 17h00
2024-2025
Course Schedule
Date Subject
1. Fundamentals of Material Balances
13-Sep 1.1. Process definition and classification
1.2. Material balance calculations
20-Sep 1.3. Balances on multiple-unit processes
27-Sep Review on Mass Balances (non-reactive)
1.4. Chemical reaction stoichiometry
04-Oct
1.5.1 Balances on reactive processes (part 1)
1.5.2 Balances on reactive processes (part 2)
11-Oct 1.6. Balances on multiple unit reactive processes
Review on Mass Balances (non-reactive & reactive)
2. Energy and Energy Balances
18-Oct 2.1. Energy balances on closed systems Recommended textbook:
2.2. Open systems at steady state Elementary Principles of Chemical
3. Balances on Non-Reactive Processes Processes
3.1. Energy balance calculation Richard M. Felder & Ronald W.
01-Nov
3.2. Changes in Pressure, Temperature, Phases Rousseau
3.3. Mixing and Solution

4. Balances on Non-Reactive Processes

08-Nov
Problems: Mass and Energy Balances on non-Reactive Systems

15-Nov Midterm Exam: Mass & Energy Balances non-Reactive Systems

22-Nov Review Midterm
5. Balances on Reactive Processes
5.1. Heats of reaction/combustion
29-Nov 5.2. Combustion reactions
5.3. Enthalpy of reaction
5.4. Energy balance calculation
6. Energy balances on mixing processes
06-Dec
Review
13-Dec Review and Study Session
 Session V: Friday 18 October 2024

After studying this session you will be able to:

1. Understand the concepts of work and heat (signs!), intrinsic and

extensive properties

2. Identify non-reactive closed systems & Define an energy balance

on them

3. Identify non-reactive open systems & Define an energy balance

on them
1. Introduction
 Introduction to energy balances

By performing energy balances, we answer questions like:

• How much energy is required for pumping 1000 m3/h?
• What is the rate of energy supply in a distillation column?
• A→B exothermic and 75% conversion @400k, what is the rate of energy
removal to achieve the target?
• …
• Is there a cheaper way of achieving my process specifications? → Energy
is expensive!!!

In the design of a process, we must account for:

✓ the flow of energy into and out of each process unit
✓ the overall energy requirement of the process
Recalling the definition of a system

Flow of mass
 Recalling the definition of a system

Flow of mass

Open Closed
 Recalling the definition of a system

Flow of mass Flow of energy

Open Closed
 Recalling the definition of a system

Flow of mass Flow of energy

Open Closed Adiabatic Diathermic

 Recalling the definition of a system

Flow of mass Flow of energy

Open Closed Adiabatic Diathermic

Closed + Adiabatic Closed + Diathermic

 Forms and Transfer of energy of a system
The total energy of a system has 3 forms

1 Kinetic energy 2 Potential energy 3 Internal energy

Energy associated with movement Energy in a potential field “Everything else”
Gravitational, electromagnetic, … Molecular energy …
 Forms and Transfer of energy of a system
The total energy of a system has 3 forms

1 Kinetic energy 2 Potential energy 3 Internal energy

Energy associated with movement Energy in a potential field “Everything else”
Gravitational, electromagnetic, … Molecular energy …

The energy is transferred from the environment to a process system

(and vice-versa) in 2 ways

A Heat (Q): flow or exchange of B Work (W): flow or exchange of

energy due to ΔΤ energy due to “driving forces”
• Could enter the system via other than temperature (e.g.:
conduction, convection, or voltage, force)
radiation • Could be done on, or by, the
system
 Clarifications
• Q, W are transferred energies: a system does not
possess heat or work

• Signs of Q and W according to this course conventions:

 Clarifications
• Q, W are transferred energies: a system does not
possess heat or work

• Signs of Q and W according to this course conventions:

o Q>0 : heat entering the system
Heat is positive because the system in effect gains energy when heat enters
o Q<0 : heat leaving the system
 Clarifications
• Q, W are transferred energies: a system does not
possess heat or work

• Signs of Q and W according to this course conventions:

o Q>0 : heat entering the system
Heat is positive because the system in effect gains energy when heat enters
o Q<0 : heat leaving the system

o W>0 : work done BY the system

o W<0 : work done ON the system
The choice for the sign of work is arbitrary but facilitates the reading of the
expression of energy transferred to the system (see next slides):

Etransferred = Q - W
 Types of work

• Wm : mechanical work which is due to movement of the boundary, (e.g.,

piston)
• Wel : electrical work (e.g., electrical generator)
• Ws : shaft work (e.g., mixing, turbine, pump)
• Wfl : flow work
• Work done to push a fluid into system (use example of pistons moving fast)
• Work done to push fluid out of system

Example 1: Determine the sign of the work transferred to the system in the following cases:
• a piston compress the system
• a generator gives energy to the system
• a pump applies work into a stream (system)
• a turbine acts on a stream (system)
• a fluid (system) flows into a piston
 Classification of properties
• Intensive property: is a physical property of a system that does not
depend on the system size or the amount of material in the system.
E.g.: density, P, T

• Extensive property: is a property that is directly proportional to the

amount of material in the system.
E.g.: mass and volume, internal energy (U)

• Specific property: is a property that depends on, or is calculated based on,

another measurable property, and are denoted with a “ˆ”.
E.g.: density is considered 'specific’ because it can be calculated from volume
and mass

How to calculate an extensive property for the whole system?

• for internal energy of the system: U(J) = m (kg) Û (J/kg)
• for the continuous flow: Ů(J/s) = ṁ (Kg/s) Û (J/kg)
 Defining the energy balance on a system
Recall the mother of all equations for conservation of mass:
Acc = In - Out + Gen - Cons
 Defining the energy balance on a system
Recall the mother of all equations for conservation of mass:
Acc = In - Out + Gen - Cons

Law of conservation of energy:

This states that: if E is the entire amount of energy in the system,
then:

E accumulated = E input ‒ E output + E gen + E transferred

 Defining the energy balance on a system
Recall the mother of all equations for conservation of mass:
Acc = In - Out + Gen - Cons

Law of conservation of energy:

This states that: if E is the entire amount of energy in the system,
then:

E accumulated = E input ‒ E output + E gen + E transferred

E in = Σ input streams mjÊj , Eout = Σoutput streams mjÊj

E transferred = Q - W
Q: heat transferred to the system from its surrounding (+ sign: gain of energy)
W: work done by system on its surrounding (+ sign so that –W is negative)
 Energy balances overview
Depending on the system under study, the energy balance equation
will simplify:

E accumulated = E input ‒ E output + E gen + E transferred

unsteady-
Closed state
systems
steady-state
Non-reactive
Energy systems unsteady-
Balance Reactive Open state
systems systems
steady-state
2. Energy balances on closed non-reactive systems
 Energy balances on closed non-reactive systems

The simplest case consists in closed systems:

unsteady-
Closed state
systems
steady-state
Non-reactive
Energy systems unsteady-
Balance Reactive Open state
systems systems
steady-state
 Energy balances on closed non-reactive systems

The simplest case consists in closed systems:

unsteady-
Closed state
systems
steady-state
Non-reactive
Energy systems unsteady-
Balance Reactive Open state
systems systems
steady-state

E accumulated = E input ‒ E output + E gen + E transferred

 Energy balances on closed non-reactive systems

The simplest case consists in closed systems:

unsteady-
Closed state
systems
steady-state
Non-reactive
Energy systems unsteady-
Balance Reactive Open state
systems systems
steady-state

E accumulated = E input ‒ E output + E gen + E transferred

E accumulated = E transferred
 Energy Balance on a Closed System
E accumulated = E input ‒ E output + E gen + E transferred

E accumulated = E transferred = ΔE Q

W
ΔE = Q – W
 Energy Balance on a Closed System
E accumulated = E input ‒ E output + E gen + E transferred

E accumulated = E transferred = ΔE Q Closed system

E = U+K+P
W
ΔE = Q – W

The total energy (E) may be regarded as composed of many forms. Obvious contributions to
the total energy arise from the internal, kinetic and potential energies

Q−W = ΔU + ΔEk + ΔEp

• ΔEp is change in potential energy

• Q is heat transferred to the system
• If the system is adiabatic, there is neither gain by the system not heat loss and Q is zero
• W is work done by the system
• If there are no moving parts, then W=0
Example: Energy Balance on a Closed System
1 mole of gas contained in a cylinder fitted with movable position:
The cylinder is placed in boiling water and
I) Equilibrated: to 100 ℃

250C 1000C

Initial state Final state

II) The piston is then released, and the gas does 100 J of work to move the piston
to its new equilibrium position.
The final gas temperature is 100 ℃

100 0C 1000
C

Initial state Final state

Write and solve energy balances. For two stage with assuming:
• No changes in m, Ek & Ep
• Ideal gas
• Ĉv = 2 kcal.mol-1.k-1
Example: Energy Balance on a Closed System (Continued)
I) E accumulated = E input ‒ E output + E gen + E transferred

E accumulated = E transferred

ΔU + ΔEk + ΔEp = Q−W 250C 1000C

Initial state Final state

m ΔÛ + m ΔÊk + m ΔÊp = Q - W
0 0 0
m (Ûf – Ûi) + m (Êk,final – Êk, initial) + m (Êpf – Êpin) = Q – W

m (Ûf – Ûi) = m ΔÛ = Q

ΔÛ = Ĉv (ΔT) = 2. 75 k = 150 kcal = 627.6 kJ

Ĉv for 1 mol of gas= 2 kcal.mol-1.k-1 . 1 mol = 2 kcal.k-1

II) Ufinal = Uinitial , because ΔT = 0

0 0 0
ΔU + ΔEk + ΔEp = Q – W boundaries move so W =/= 0!

100 0C 1000C
⇒ 0 = Q – W ⇒ Q = W = 100 J > 0
Initial state Final state
What does Q > 0 mean? The system further absorbs
energy in form of heat to do work
 Examples of closed systems

W=5kJ
Qout=2kJ

ΔE=8 kJ
ΔE=5 kJ
Qin=10kJ

Heating water in a closed

Compressing a gas in a
vessel
cylinder
unsteady-
unsteady-
state
state
Closed
Closed
systems
systems
steady-state
steady-state
Non-reactive
Non-reactive W=5kJ
systems
systems Qout=10kJ
Energy
Energy unsteady-
unsteady-
Balance
Balance state
state
Reactive
Reactive Open
Open
systems
systems systems
systems ΔE=0 kJ
steady-state
steady-state Q=5kJ ΔE=0 kJ
Qin=10kJ

Heating water in a closed

Compressing a gas in a
vessel
cylinder
3. Energy balances on open non-reactive systems
Energy balances on open non-reactive systems

unsteady-
Closed state
systems
steady-state
Non-reactive
Energy systems unsteady-
Balance Reactive Open state
systems systems
steady-state

E accumulated = E input ‒ E output + E gen + E transferred

 Energy Balance on an Open System
A system is open if mass crosses the system boundary

Q W

Mass In Mass out

E1 E2

law of conservation of energy:

E accumulated = E input ‒ E output + E gen + E transferred

E in = Σ input streams mjÊj , Eout = Σoutput streams mjÊj

E transfer = Q – W

msys Êacc = min Ê1 - moutÊ2 + Q - W

(hat indicates energy per unit mass)
 Energy Balance on an Open System
(Continuation) Energy Balance on an Open System
Q W
msysÊacc = min Ê1 -mout Ê2 + Q -W
Mass In Mass out
E1 E2

• For such a system, work must be done on the fluid mass to push it into
the system; flow work
• Work could also be done by the fluid mass on moving parts of the
system (example: steam driving a turbine); shaft work
W = Ws + Wfl
.
Accumulation=0
m1 (Û1 + Êk1 + Êp1 ) - m2 (Û 2 + Êk 2 + Êp2 )+ Q - (Ws + Wfl )
m1 = m2 = m .

if Ws, Ek, Ep =0
m DÛ + Q -Wfl = 0
 What is Wfl?

Work required to push the mass in = Pin Vin (N/m2 * m3 =N.m=J)

Work done by the fluid exiting the system = PoutVout
The net rate of work done by the system = Wfl = PoutVout - Pin Vin

. . . . .
m DÛ + Q -Wfl = m1 Û1 - m2 Û2 + Q - Pout Vout + Pin Vin = 0

Pout Vout → Work done by system to push out

Pin Vin → Work done on system by pushing in
 Definition of Enthalpy
. . Definition
. . of Enthalpy
.
m DÛ + Q -Wfl = m1 Û1 - m2 Û2 + Q - Pout Vout + Pin Vin = 0

ṁ1 Û1 ‒ ṁ2 Û2 + Q - m2 P2V̂2 + m1P1V̂1 = 0

⇒ m1 (Û1 + P1V̂1 )- m2 (Û2 + P2V̂2 )+Q = 0

Û + P V̂ = ? Þ Û + P V̂ = Ĥ

m1Ĥ1 - m2 Ĥ 2 +Q = 0
 Definition of Enthalpy
Definition of Enthalpy
Û + P V̂ = ? Þ Û + P V̂ = Ĥ m1Ĥ1 - m2 Ĥ 2 +Q = 0

• So, using the enthalpy of streams takes into account the Wfl for streams
in open systems

• Û is specific internal energy, P is pressure, and V̂ is specific volume

• It is not possible to know or estimate the absolute values of internal
energy and enthalpy. We need to find only the change in these
properties to make an energy balance
• The general energy equation for an open system with flow work, shaft
work, kinetic energy changes, potential energy changes and heat transfer
becomes:

DH + DEk + DEP = Q -Ws

Remarks Remarks

Closed system : ∆U + ∆Ek + ∆Ep = Q – W

Open system: DH = Σout ṅi Ĥi –Σin ṅi Ĥi or DH = Σout ṁi Ĥi –Σin ṁi Ĥi

Open system : DH + DEk + DEP = Q -Ws

∆U only depends on the temprature:

so for constant T: ∆U = 0 → ∆H = ∆U + ∆(PV) = V∆P

For the ideal gas, liquds and solids:

• For the solids and liquds : Cp = Cv

• For the gases : Cp = Cv + R (from thermodynamics course!)
 Example: Energy balance on an open
Example 3: Energy balance on an open system
system

Ice, 0°C, 1atm water, 100°C, 1atm

The process is st.st and it reach to a final stable situation

Q = ? Kcal / min kg H2O

DH + DEk + DEP = Q -Ws

ṁout Ĥout – ṁin Ĥin = Q

→ Q/ṁ = Ĥout – Ĥin

For a system with one flux in and one flux out without any accumulation:
the mass in the system ṁin = ṁout = ṁ
 Q /ṁ = Ĥout – Ĥin

• To get the thermodynamic properties

• using the tables, for a substrate by knowing T and P, we get (Ĥ, Û, V, Ĉp, Ĉv)
• given information for the reference state (P,T)

Species ṁin (mole/h) Ĥ in (KJ/mole) ṁout (mole/h) Ĥ out (KJ/mole)

H 2 O(s) ṁ1 Ĥ water(s) (Ĥ 1 ) – –
H 2 O(l) – – ṁ2 Ĥ water(l) (Ĥ 2 )

• We need a reference state to calculate Ĥ for the corresponding T and P

• Ĥ1= ∆Ĥ1 + ∆Ĥ2
• Ĥ2 = ∆Ĥ3
Water
Ĥ2 P= 1 atm, T= 1000C
Ice
P= 1 atm Q
Ĥ1
∆Ĥ2= Ĥlatente

Ĥref (Liquid, 250C, 1 atm)

Example: Energy balance on a NR Open System
Example 1: Energy balance on a NR Open System
A mixture of Acetone and Nitrogen is entering in a cooling system (condenser) to
separate the Acetone. based on the information given on the flowchart, calculate
the Q needed to be removed from the system for this separation process.

36.45 mol/s
0.092 mol Ac(v)/mol
Q? 0.908 mol N2/mol
20 0C, 5 atm
100 mol/s
0.669 mol Ac(v)/mol Condensateur
0.331 mol N2/mol
65 0C, 1 atm
63.55 mol Ac(l)/s
20 0C, 5 atm

1. Mass balance : already done

2. From the general energy balance equation to the simplified system energy
balance equation

(∆Ek = 0, ∆Ep = 0, Ẇs = 0) Ù Ù

DH + DEk + DEP = Q -Ws Q= DH =å ni H i -å ni H i

out in
 In = 100 mol/s Q? Out1 = 36.45 mol/s
0.669 mol Ac(v)/mol 0.092 mol Ac(v)/mol
0.331 mol N2/mol 0.908 mol N2/mol
650C, 1 atm Condensateur 200C, 5 atm

Out2 = 63.55 mol Ac(l)/s

200C, 5 atm
3. Reference states (for each specie in the system):
Ac (liq, 20°C, 5atm), N2 (gas, 25°C, 1atm)

4. Open systems → inlet-outlet enthalpy table

Species ṅin (mol/s) Ĥ in (kJ/mol) ṅout (mol/s) Ĥ out (kJ/mol)
Ac(v) 66.9 Ĥ1 3.35 Ĥ3
Ac(l) – – 63.55 0
N2 33.1 Ĥ2 33.1 Ĥ4

All the species in INLET stream(s): OUTLET stream(s):

the system Flowrates and specific Flowrates and specific
enthalpies* enthalpies*

* Ĥi (specific enthalpy of specie i): should be calculated at the state of that specie
in the inlet and outlet streams
 5. Construct process paths: calculate the specific enthalpies

5. A) Ac(v) in INLET STREAM: Final state (stream IN):

Ac (v, 65°C, 1atm)
Ĥ1
∆Ĥ1d

Ac (v, 56°C, 1atm)

Reference state:
Ac (l, 20°C, 5atm) ∆Ĥ1c (latent heat at 56°C)
∆Ĥ1a
∆Ĥ1b
Ac (l, 20°C, 1atm) Ac (l, 56°C, 1atm)

Ĥ1 = ∆Ĥ for Ac (l,20°C, 5atm) → Ac (v, 65°C, 1atm)

Ĥ1 = ∆Ĥ1a + ∆Ĥ1b + ∆Ĥ1c + ∆Ĥ1d

Recalling: Enthalpy and internal energy are state properties. In other words, the change in enthalpy of a
specie depends only on the final and initial states and not on how the final state is reached from the initial
state, they are path independent
 ∆Ĥ1a ∆Ĥ1b ∆Ĥ1c
Ac (l, 20°C, 5atm) Ac (l, 20°C, 1atm) Ac (l, 56°C, 1atm)
∆Ĥ1d
Ac (v, 56°C, 1atm) Ac (v, 65°C, 1atm)
CHANGE IN PRESSURE AT CONSTANT TEMPERATURE (LIQUID PHASE → CONSTANT VOLUME):

∆Ĥ1a = V̂ ∆P (the specific gravity of Ac is 0.791 and the MW is 0.058 kg/mol ,

so V̂ = 0.0734 L/mol)

Pay attention to units! to find ∆Ĥ1a in KJ/mol, V̂ should be in m /mol and ∆P in Pa

3

CHANGE IN TEMPERATURE AT CONSTANT PRESSURE (LIQUID PHASE):

o from table B.2: Ac (l) : Cp (kJ/mol °C) = 0.123 + 18.6 × 10-5 T, for T in °C

∆Ĥ1b =

CHANGE OF STATE (LATENT HEAT) AT CONSTANT PRESSURE AND TEMPERATURE:

∆ Ĥ1c = 30.2 kJ/mol (latent heat at boling point, from Table B.1)
CHANGE IN TEMPERATURE AT CONSTANT PRESSURE (GAS PHASE):
o from table B.2: Ac (v) : Cp (kJ/mol°C) = 0.07196 + 20.10 × 10-5 T – 12.78 × 10-8 T2 + 34.76 × 10-12 T3

∆Ĥ1d =
Ĥ1 = (-0.0297 + 4.68 + 30.2 + 0.753) = 35.6 kJ/mol
5. A) N2 in INLET STREAM:

Ĥ2 = ∆ Ĥ for N2 (g, 25°C, 1atm) → N2 (g, 65°C, 1atm)

CHANGE IN TEMPERATURE AT CONSTANT PRESSURE (GAS PHASE):
From Table B.2: C p,N2,g = 0.029 + 0.2199 × 10-5T + 0.5723 × 10-8T2 – 2.871 × 10-2T3

Ĥ2 =

5. B) Ac(v) in OUTLET STREAM:

CHANGE OF STATE (LATENT HEAT) AT CONSTANT PRESSURE AND TEMPERATURE:
Ĥ3 = ∆Ĥ for Ac (l, 20°C, 5atm) → Ac (v, 20°C, 5atm)
Ĥ3 = 32 kJ/mol (creating a path, since we only have the latent heat at the b.p.)

5. B) N2 in OUTLET STREAM:
Ĥ4 = ∆Ĥ for N2 (g, 25°C, 1atm) → N2 (g, 20°C, 5atm)
Ĥ4 = N2 (g, 25°C, 1atm) → N2 (g, 20°C, 1atm) → N2 (g, 20°C, 5atm)
CHANGE IN TEMPERATURE AT CONSTANT PRESSURE (GAS PHASE):

Ĥ4 =

CHANGE IN PRESSURE AT CONSTANT TEMPERATURE (GAS PHASE):

For N2 (g, 20°C, 1atm) → N2 (g, 20°C, 5atm) there is a very small change of enthalpy that can be
neglected
6. Solve the simplified energy balance equation:

Ù Ù
Q= DH =å ni H i -å ni H i
out in

Species ṅin (mol/s) Ĥ in (kJ/mol) ṅout (mol/s) Ĥ out (kJ/mol)

Ac(v) 66.9 Ĥ 1 = 35,6 3.35 Ĥ 3 = 32
Ac(l) – – 63.55 0
N2 33.1 Ĥ 2 = 1,16 33.1 Ĥ 4 = -0,1

[(3.35) (32.0) + (63.55) (0) + (33.1) (– 0.10)] kJ/s + …

… – [(66.9) (35.6) + (33.1) (1.16)] kJ/s = – 2320 kJ/s

DH = Q = – 2320 kJ/s = – 2320 kW

 Thermodynamics data
Thermodynamics data

• Enthalpy and internal energy are state properties. In other words, the change in
enthalpy of a species depends only on the final and initial states and not on how
the final state is reached from the initial state, they are path independent

• Enthalpy and internal energy of species could be tabulated with respect to a

reference state (temperature, pressure and phase)

• There are “tables” at the end of the book that the thermodynamic properties
can be looked up from them instead of calculating them every time

• You should get used to knowing how to read these tables!!

 Procedure for Energy Balance Calculations
1. Make material balance calculations and find flow rates (or masses) of all streams

2. Write the generalized energy balance equation and cancel all the terms that are either zeros
or can be neglected

3. Choose reference states for each specie involved. By reference state we mean T, P and the
phase of the species. A proper choice of the reference states enables easy calculation of
enthalpies and hence, energy balances

4. For open systems: construct an inlet-outlet enthalpy table with mass or molar flow rates
For closed systems: the table should contain initial-final amounts of species and internal
energies

5. Estimate the specific enthalpies or internal energies and insert the values in the Table
constructed in step 4. You need to construct process paths to determine specific enthalpies
and internal energies

6. Solve the simplified energy balance equation (from step 2) and calculate the unknowns