CHEMICAL ENGINEERING PRINCIPLES

CHE 202

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TEXTBOOK: Felder’s Elementary Principles of Chemical Processes 4th
ed. GE, Richard M. Felder; Ronald W. Rousseau; Lisa G.
Bullard, Wiley
Grading:
20% homeworks and quizzes
20% first test
20% second test
40% final examination
No makeup tests will be given
Office # 2B44
Office hours: posted on door

11/27/2023 Chemical Engineering Principles. Abasaeed 2

 ENERGY AND ENERGY BALANCES

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 Forms of Energy
First Law of Thermodynamics
1- Kinetic Energy (𝐸𝑘 ): due to movement of the system (velocity related)
1
𝐸𝑘 = 𝑚 𝑢2 (500001)
2
where: m=mass ; u=velocity. Depending on the units, one may need to use the
conversion factor gc
1 𝑘𝑔 𝑚Τ𝑠 2 32.174 𝑙𝑏𝑚 𝑓𝑡Τ𝑠 2
𝑔𝑐 = = (500002)
1𝑁 1𝑙𝑏𝑓

2- Potential Energy (𝐸𝑝 ): due to the position of the system (height related)
𝐸𝑝 = 𝑚 𝑔 𝑧 (500003)

where: g=gravity ; z=height measured from a reference point. Also, the conversion
factor gc may be needed.

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Example (500001): Kinetic Energy Transported by a Flowing Stream.

Water flows into a process unit through a 2-cm ID pipe at a rate of 2 𝑚3 Τℎ.
Calculate 𝐸𝑘 for this stream in joules/second
𝑣𝑜𝑙𝑢𝑚𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒
𝑢= = 1.77 𝑚Τ𝑠
𝑋 − 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎
𝑚 = 𝑣 × 𝜌 = 0.556 𝑘𝑔Τ𝑠
1
𝐸𝑘 = 𝑚 𝑢2 = 0.87 𝐽Τ𝑠
2 𝑔𝑐

Example (500002) Potential Energy Increase of a Flowing Fluid

Crude oil is pumped at a rate of 15 𝑘𝑔Τ𝑠 from a point 220 meters below the earth's
surface to a point 20 meters above ground level. Calculate the attendant rate of
increase of potential energy.
∆𝐸𝑝 = 𝑚 𝑔 ∆𝑧 = 15 × 9.81 × 20 − (−200)
∆𝐸𝑝 = 35300 𝐽Τ𝑠 = 35.3 𝑘𝐽Τ𝑠

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 Forms of Energy
3- Internal Energy (𝑈): All energy possessed by the system other than 𝐸𝑘
and 𝐸𝑝 (i.e., energy related to the motion of molecules relative to the center
of mass of gravity of the system. It includes motions such as: vibrational,
rotational, and electromagnetic motion of the molecule and the atomic
interactions)
Note: Kinetic, potential, and internal energies are confined within the
system, i.e., can’t be exchanged with the surroundings
4- Heat (𝑄): due to temperature difference between the system and the
surroundings, heat energy may be transferred to or from the system. If Q is
added to the system, it is taken to be positive; else negative.
5- Work (W): due to mixing or presence of a moving part, work can be
exchanged between the system and its surroundings. If W is done by the
system on the surroundings, it is taken to be positive; else negative.

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First Law of Thermodynamics (closed System)

𝑄 − 𝑊 = ∆𝑈 + ∆𝐸𝑘 + ∆𝐸𝑝 (500004)

1. The internal energy of a system
∆𝑈 = 𝑓(chemical composition, state of aggregation, and temperature)
∆𝑈 ≠ 𝑓(pressure for ideal gases, liquids, and solids)
If no temperature changes, phase changes, or chemical reactions occur in a closed
system and if pressure changes are less than a few atmospheres, then ∆𝑈 ≈ 0.
2. If a system is not accelerating, then ∆𝐸𝑘 = 0.
3. If a system is not rising or falling, then ∆𝐸𝑝 = 0
4. If a system and its surroundings are at the same temperature or the system is
perfectly insulated, then 𝑄 = 0. The process is then termed adiabatic.
5. If there are no moving parts or electrical currents or radiation at the system
boundary, then 𝑊 = 0.
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Example (500003) Energy Balance on a Closed System

A gas is contained in a cylinder fitted with a movable piston. The initial gas
temperature is 25°C. The cylinder is placed in boiling water with the piston held in a
fixed position. Heat in the amount of 2.00 kcal is transferred to the gas, which
equilibrates at 100°C (and a higher pressure). The piston is then released, and the
gas does 100 J of work in moving the piston to its new equilibrium position. The
final gas temperature is 100°C.

Write the energy balance equation for each of the two stages of this process, and in
each case solve for the unknown energy term in the equation. In solving this
problem, consider the gas in the cylinder to be the system, neglect the change in
potential energy of the gas as the piston moves vertically, and assume the gas
behaves ideally. Express all energies in joules

Solution (500003)

Stage 1: piston held in position; Tinitial= 25°C; Tfinal = 100°C; Q=2 kcal 
𝑊 = 0 𝑛𝑜 𝑚𝑜𝑣𝑖𝑛𝑔 𝑝𝑎𝑟𝑡 ; ∆𝐸𝑘 = 0 𝑠𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑟𝑦 + ∆𝐸𝑝 = 0 (𝑛𝑜 𝑑𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡)
∴ 𝑄 = ∆𝑈 = 2 𝑘𝑐𝑎𝑙 = 8370 𝐽

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Solution (500003)

Stage 2: piston released; W = 100 J; Tinitial= 100°C; Tfinal = 100°C 

∆𝑈 = 0 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇 ; ∆𝐸𝑘 = 0 𝑠𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑟𝑦 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑎𝑛𝑑 𝑓𝑖𝑛𝑎𝑙𝑙𝑦 + ∆𝐸𝑝 = 0 (𝑛𝑒𝑔𝑙𝑒𝑐𝑡)
∴ 𝑤 = 𝑄 = 100 𝐽

Intensive and Extensive Properties

Intensive properties are independent of the quantity (or volume) of the material
(e.g., temperature, pressure, density …. etc).

Extensive properties depend on the quantity (or volume) of the material (e.g., mass
flow rate; kinetic and potential energy….. etc)

Definitions

Shaft Work and Flow Work

Ws = shaft work is work done on or by system

Wf = flow work is work done by and on the fluid within the system
𝑊𝑓 = ∆ 𝑃𝑉 = 𝑃2 𝑉2 − 𝑃1 𝑉1 (500005)
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Enthalpy (H)
𝐻 = 𝑈+𝑃𝑉 (500006)
∆𝐻 = ∆𝑈 + ∆(𝑃 𝑉)
෡
Specific Enthalpy (𝑯)
𝐻 𝐽 𝐻 𝑗
෡=
𝐻 = (500007)
𝑚 𝑘𝑔 𝑛 𝑚𝑜𝑙
෡=𝑈
𝐻 ෡ + 𝑃 𝑉෠ (500008)
Example (500004): Calculation of Enthalpy
The specific internal energy of helium at 300K and 1 atm is 3800 J/mol , and the specific
molar volume at the same temperature and pressure is 24.63 L/mol. Calculate the specific
enthalpy of helium at this temperature and pressure, and the rate at which enthalpy is
transported by a stream of helium at 300 K and 1 atm with a molar flow rate of 250 kmol/h
Solution (500004)
Equ. (500008) Note: must unify the units 
8.314 𝐽
෡ = 3800 + 1 × 24.63
𝐻 = 6295.4
0.08206 𝑚𝑜𝑙
𝐽
𝐻 = 6295.4 × 250000 = 1.574 × 109
ℎ
𝐽
𝐻 = 4.372 × 102
𝑠

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Note: Enthalpy is a relative quantity (i.e., has no absolute value) like the height it
has to be measured from a reference point. The reference for the enthalpy requires
determining (fixing) 3 three things. (1) state of aggregation, (2) temperature, and (3)
pressure.

Energy Balances on Open Systems at Steady State

𝑄 − 𝑊𝑠 = ∆𝐻 + ∆𝐸𝑘 + ∆𝐸𝑝 (500009)

Example (500005): Energy Balance on a Turbine

Five hundred kilograms per hour of steam drives a turbine. The steam enters the
turbine at 44 atm and 450°C at a linear velocity of 60 𝑚Τ𝑠 and leaves at a point 5 m
below the turbine inlet at atmospheric pressure and a velocity of 360 𝑚Τ𝑠. The
turbine delivers shaft work at a rate of 70 kW, and the heat loss from the turbine is
estimated to be 104 𝑘𝑐𝑎𝑙 Τℎ. Calculate the specific enthalpy change associated with
the process.
Solution (500005)
1
Equ. (500001)  ∆𝐸𝑘 = 𝑚 ∆𝑢2 = 8.75 𝑘𝑊
2𝑔𝑐
𝑔
Equ. (500003)  ∆𝐸𝑝 = 𝑚 ∆𝑧 = −6.81 × 10−3 𝑘𝑊
𝑔𝑐
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Solution (500005) continued:
Convert Q to kW  𝑄 = −104 𝑘𝑐𝑎𝑙 Τℎ = −11.6 𝑘𝑊
Equ. (500009)  ∆𝐻 = 𝑄 − 𝑊𝑠 − ∆𝐸𝑘 − ∆𝐸𝑝
∆𝐻 = −11.6 − 70 − 8.75 − 6.81 × 10−3 = 90.36 𝑘𝑊
∆𝐻 −90.36 𝑘𝐽
෡
∆𝐻 = = = 650.6
𝑚 500/3600 𝑘𝑔
Enthalpy Calculations
The enthalpy can be determined from tables
or equations. Since enthalpy is a relative
quantity one must:
1- Know or set the reference point
2- Know in which region the material falls 
e.g., see figure where the material goes
from liquid to vapor state (e.g., H2O where
the saturation temperature, Ts, at 1 atm is
100ºC)
1- Region (1) is called subcooled liquid and
is characterized by T<Ts

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Enthalpy Calculations
2- Point (2) is saturated liquid at 1 atm and 100ºC (T=Ts)
3- Region (3) is a 2-phase region (as latent heat is added liquid becomes vapor).
The % of liquid or vapor can be calculated (quality)
4- Point (4) is saturated vapor at 1 atm and 100ºC (T=Ts)
5- Region (5) is called superheated vapor and is characterized by T>Ts
6- The maximum point on the curve is called the critical point where the saturated
vapor curve (to right) meet with the saturated liquid curve (to the left)
7- Region above the critical point is called supercritical fluid.

H2O figure for all 3-phase shows

the triple point
(solid, liquid, and vapor exist together)

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Enthalpy Calculations from Tables
For example, the table for saturated methyl chloride is given below

State T(ºF) P(psia) ෡ (𝒇𝒕𝟑 Τ𝒍𝒃𝒎 )

𝑽 ෡ (𝑩𝒕𝒖Τ𝒍𝒃𝒎)
𝑯
Liquid -40 6.878 0.01553 0.00
Vapor 0 18.90 4.969 196.23
Vapor 50 51.99 1.920 202.28

A quick look at the table 

1- reference point is where 𝐻෡ = 0  (liquid, -40, 6.878)
2- ∆𝐻෡ 𝑣𝑎𝑝𝑜𝑟, 50, 51.99 𝑡𝑜 𝑣𝑎𝑝𝑜𝑟, 0, 18.9 = 196.23 − 202.28 = −6.05 𝐵𝑢𝑡/𝑙𝑏𝑚
3- ∆𝐻෡ 𝑙𝑖𝑞𝑢𝑖𝑑, −40, 6.878 𝑡𝑜 𝑣𝑎𝑝𝑜𝑟, 50, 51.99 = 202.28 − 0.0 = 202.28 𝐵𝑢𝑡/𝑙𝑏𝑚
4- ∆𝑈෡ 𝑣𝑎𝑝𝑜𝑟, 50, 51.99 𝑡𝑜 𝑣𝑎𝑝𝑜𝑟, 0, 18.9 = ∆𝐻 ෡ − ∆ 𝑃 𝑉෠
1.987 𝐵𝑡𝑢
෡ = −6.05 −
∆𝑈 18.9 × 4.969 − 51.99 × 1.92 = −4.96 𝐵𝑢𝑡/𝑙𝑏𝑚
10.73 𝑓𝑡 3 . 𝑝𝑠𝑖𝑎

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Steam Tables
1- Saturated steam (Tables B5 and
B6)
2 4 2 4 2 4
2- Superheated steam (Table B7)

Saturated Steam –B5

Temperature based 
Ref (water, 0.01, 0.00611)

𝐻෡ 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚 , 20°𝐶 = 2538.2 𝑘𝐽/𝑘𝑔

𝑉෠ 𝑠𝑎𝑡. 𝑣𝑎𝑝𝑜𝑟, 40°𝐶 = 19.55 𝑚3 /𝑘𝑔
𝑈 𝑠𝑎𝑡. 𝑤𝑎𝑡𝑒𝑟, 30°𝐶 = 125.7 𝑘𝐽/𝑘𝑔
𝐻෡ 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚 , 33.5°𝐶 =? 𝑘𝐽/𝑘𝑔 
interpolate between (32 and 34)
𝒚𝟐 − 𝒚𝟏
𝒚 = 𝒚𝟏 + 𝒙 − 𝒙𝟏
𝒙𝟐 − 𝒙𝟏
𝟐𝟓𝟔𝟑. 𝟔 − 𝟐𝟓𝟔𝟎
෡ = 𝟐𝟓𝟔𝟎 +
𝐻 𝟑𝟑. 𝟓 − 𝟑𝟐
𝟑𝟒 − 𝟑𝟐
෡ 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚 , 33.5°𝐶 = 2562.7 𝑘𝐽/𝑘𝑔
𝐻

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Steam Tables 2 4 2 4 2 4

Saturated Steam –B6

Pressure based 
Ref (water, 0.01, 0.00611)

෡ 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚 , 0.14 𝑏𝑎𝑟 = 2596.2 𝑘𝐽/𝑘𝑔

𝐻
𝑉෠ 𝑠𝑎𝑡. 𝑣𝑎𝑝𝑜𝑟, 0.2 𝑏𝑎𝑟 = 7.65 𝑚3 /𝑘𝑔
෡ 𝑠𝑎𝑡. 𝑤𝑎𝑡𝑒𝑟, 0.06 𝑏𝑎𝑟 = 151.5 𝑘𝐽/𝑘𝑔
𝑈
𝐻෡ 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚 , 0.105 𝑏𝑎𝑟 =? 𝑘𝐽/𝑘𝑔 
interpolate between (0.1 and 0.11 bar)
𝒚𝟐 − 𝒚𝟏
𝒚 = 𝒚𝟏 + 𝒙 − 𝒙𝟏
𝒙𝟐 − 𝒙𝟏
𝟐𝟓𝟖𝟖. 𝟏 − 𝟐𝟓𝟖𝟒. 𝟖
෡ = 𝟐𝟓𝟖𝟒. 𝟖 +
𝐻 𝟎. 𝟏𝟎𝟓 − 𝟎. 𝟏
𝟎. 𝟏𝟏 − 𝟎. 𝟏𝟎
෡ 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚 , 0.105 𝑏𝑎𝑟 = 2586.45 𝑘𝐽/𝑘𝑔
𝐻

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Steam Tables
Superheated Steam –B7
Column (1): Pressure (bar) and (saturation temperature, ºC)
Column (2): 𝐻 ෡ ; 𝑈 ; 𝑉෠
Column (3): Saturated liquid (point 2)
Column (4): Saturated liquid (point 4)
Inside stair-like is subcooled liquid (region 1)
Outside stair-like (to the right) is superheated vapor (region 5)
1- You need T and P to get the superheated or subcooled
2- Never interpolate between inside and outside the stairs, instead:
2-1 If you want to interpolate in region 5, use point 4 as the lowest
value.
2-2 If you want to interpolate in region 1, use point 2 as the highest
value.

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Superheated Steam –B7

2 4
5
5

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Superheated Steam –B7
Direct reading
෡ 100º𝐶, 0.1 𝑏𝑎𝑟 = 2688 𝑘𝐽/𝑘𝑔
𝐻
෡ 75º𝐶, 40 𝑏𝑎𝑟 = 313 𝑘𝐽/𝑘𝑔
𝑈

Interpolation
෡ 212º𝐶, 5 𝑏𝑎𝑟 =? 𝑘𝐽/𝑘𝑔  interpolate between (200-250º𝐶 while P=5 bar)
𝐻
2961 − 2855
෡ = 2855 +
𝐻 212 − 200 = 2880.4 𝑘𝐽/𝑘𝑔
250 − 200
෡ 212º𝐶, 5 𝑏𝑎𝑟 = 2586.45 𝑘𝐽/𝑘𝑔
𝐻

Do the same if the temperature is present in the table and the pressure is not, e.g.,
2902 − 2943
෡ 300º𝐶, 17 𝑏𝑎𝑟 = 2943 +
𝐻 17 − 10 = 2914.3 𝑘𝐽/𝑘𝑔
20 − 10

Inside and outside the stairs

One value falls inside the stairs (200ºC) and the other outside (250ºC), e.g., (use
point 4 i.e., 212.4ºC)
2902 − 2797.2
෡ 230º𝐶, 20 𝑏𝑎𝑟 = 2797.2 +
𝐻 230 − 212.4 = 2846.6 𝑘𝐽/𝑘𝑔
250 − 212.4

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Superheated Steam –B7
Triple interpolation
If both (T and P) are not present in the Table and one point falls inside
෡ 230º𝐶, 17 𝑏𝑎𝑟 =? ? ? 𝑘𝐽/𝑘𝑔
𝑈
(1) For P=10 bars
2710 − 2621
෡
𝑈 230º𝐶, 10 𝑏𝑎𝑟 = 2621 + 230 − 200
250 − 200
𝑈෡ 230º𝐶, 10 𝑏𝑎𝑟 = 2674.4 𝑘𝐽/𝑘𝑔
(2) For P=20 bars (note: one point is inside)
2679 − 2598.2
෡ 230º𝐶, 20 𝑏𝑎𝑟 = 2598.2 +
𝑈 230 − 212.4
250 − 212.4
𝑈෡ 230º𝐶, 20 𝑏𝑎𝑟 = 2636 𝑘𝐽/𝑘𝑔
(3) For T=230ºC  fix P
2636 − 2674.4
෡
𝑈 230º𝐶, 17 𝑏𝑎𝑟 = 2674.4 + 17 − 10
20 − 10
𝑈෡ 230º𝐶, 17 𝑏𝑎𝑟 = 2647.8 𝑘𝐽/𝑘𝑔
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Example (500006) Energy Balance on a Steam Turbine
Steam at 10 bar absolute with 190°C of superheat is fed to a turbine at a
rate m =2000 kg/h. The turbine operation is adiabatic, and the effluent is
saturated steam at 1 bar. Calculate the work output of the turbine in
kilowatts, neglecting changes in kinetic and potential energy.

Solution (500006)
MB  𝑚1 = 𝑚2 = 2000 𝑘𝑔Τℎ
Adiabatic  Q=0
Neglecting kinetic and potential energies 
−𝑊𝑠 = ∆𝐻 = 𝐻2 − 𝐻1
with 190°C of superheat  T1 = Ts + 190 = 370°C
Interpolation (350º𝐶 - 400º𝐶 ) and 10 bar
෢1 370º𝐶, 10 𝑏𝑎𝑟 = 3201 𝑘𝐽/𝑘𝑔
𝐻
෢2 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚, 1 𝑏𝑎𝑟 = 2675 𝑘𝐽/𝑘𝑔
𝐻
2000
−𝑊𝑠 = 2675 − 3201
3600
𝑊𝑠 = −292 𝑘𝑊

11/27/2023 Chemical Engineering Principles. Abasaeed 21

Example (500007) Energy Balance on a One-Component Process
Two streams of water are mixed to form the feed to a boiler. Process data
are as follows:
Feed stream 1:120 kg/min @ 30°C
Feed stream 2:175 kg/min @ 65°C
Boiler pressure 17 bar (absolute)

Steam emerges from the boiler through a 6-cm ID pipe. Calculate the
required heat input to the boiler in kilojoules per minute if the emerging
steam is saturated at the boiler pressure. Neglect the kinetic energies of the
liquid inlet streams.
Solution (500007)
MB  𝑚1 = 𝑚1 + 𝑚2 = 295 𝑚𝑖𝑛
Neglecting feed kinetic and potential energies; no work 
𝑄 = ∆𝐻 = 𝐻3 − 𝐻1 − 𝐻2 + ∆𝐸𝑘
Note: for input stream either P or saturated water should have been
mentioned. We will assume saturated water 

11/27/2023 Chemical Engineering Principles. Abasaeed 22

Solution (500007) continued

෢1 𝑠𝑎𝑡. 𝑤𝑎𝑡𝑒𝑟, 30º𝐶

𝐻 = 125.7 𝑘𝐽Τ𝑘𝑔
෢2 𝑠𝑎𝑡. 𝑤𝑎𝑡𝑒𝑟, 65º𝐶
𝐻 = 271.9 𝑘𝐽/𝑘𝑔
෢3 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚, 17 𝑏𝑎𝑟
𝐻 = 2793.4 𝑘𝐽Τ𝑘𝑔
෢3 𝑠𝑎𝑡. 𝑠𝑡𝑒𝑎𝑚, 17 𝑏𝑎𝑟
𝑉 = 0.1166 𝑚3 Τ𝑘𝑔

Note: 𝐸𝑘1 = 𝐸𝑘2 = 0 (assumed negligible)

1
∴ ∆𝐸𝑘 = 𝐸𝑘3 = 𝑚 𝑢32
2𝑔𝑐
𝑉ሶ 𝑚 𝑉෠ (295Τ60) × 0.1166
𝑢3 = = = 2
= 202 𝑚Τ𝑠
𝐴 𝐴 3.142 × 0.03
𝐸𝑘3 = 6.02 × 103 𝑘𝐽Τ𝑚𝑖𝑛
𝑄 = 295 × 2793.4 − 120 × 125.7 − 175 × 271.9 + 6.02 × 103

𝑄 = 7.67 × 105 𝑘𝐽Τ𝑚𝑖𝑛 = 213 𝑘𝑊

11/27/2023 Chemical Engineering Principles. Abasaeed 23

Example (500008) Energy Balance on a Two-Component Process
A liquid stream containing 60.0 mole% ethane and 40.0% n-butane is to be
heated from 150 K to 200 K at a pressure of 1 MPa. Calculate the required
heat input per kmol of the mixture, neglecting potential and kinetic energy
changes, using tabulated enthalpy data for C2H6 and C4H10, and assuming
that mixture component enthalpies are those of the pure species at the
same temperature.

Solution (500008)
Note: The materials here are ethane and n-butane NOT water, so we CAN’T
use the steam tables. Enthalpy values must be obtained from other books.
The most common book where chemical engineering needs are found is
Perry’s Chemical Engineers’ Handbook.
2 2

∴ ෡𝑗,2 − ෍ 𝑚𝑗,1 𝐻
𝑄 = ∆𝐻 = ෍ 𝑚𝑗,2 𝐻 ෡𝑗,1
𝑗=1 𝑗=1
𝑄 = 112 𝑘𝐽Τ𝑘𝑔

11/27/2023 Chemical Engineering Principles. Abasaeed 24

Example (500009) Simultaneous Material and Energy Balances
Superheated steam at 300°C and 1 atm (absolute) is to be fed to a heat
exchanger. It is produced by mixing an available stream of saturated steam
at 1 atm discharged from a turbine at a rate of 1150 kg/h with a second
stream of superheated steam at 400°C and 1 atm. The mixing may be
considered adiabatic. Calculate the amount of superheated steam at 300°C
produced and the required volumetric flow rate of the 400°C steam.

Solution (500009)
Assume 1 𝑎𝑡𝑚 ≈ 1 𝑏𝑎𝑟
MB: 𝑚3 = 𝑚1 + 𝑚2 = 1150 + 𝑚2 (A)
ONE equation, TWO unknowns 
EB: 𝑄 = ∆𝐻 = 𝑚3 𝐻 ෡3 − 𝑚1 𝐻 ෡1 − 𝑚2 𝐻
෡2
Adiabatic: 𝑄 = 0 = 3074 𝑚3 − 1150 × 2676 − 3278 𝑚2 (B)
Solving (A) and (B) simultaneously  𝑚2 = 2240 𝑎𝑛𝑑 𝑚3 = 3390 𝑘𝑔/ℎ
For stream (2), 𝑉෠2 = 3.11 𝑚3 Τ𝑘𝑔 
𝑉ሶ2 = 2240 × 3.11 = 6980 𝑚3 Τℎ

11/27/2023 Chemical Engineering Principles. Abasaeed 25

 MECHANICAL ENERGY BALANCE EQUATION
In the mechanical energy balance equation, the energy terms 𝑄 and ∆𝐻 in
the open system equation (500009) are replaced by a pressure and friction
terms. This mechanical energy balance equation suits fluid mechanics
operations (where as Equ. 500009 suits thermodynamics)
At steady state and incompressible fluid,

∆𝑃 ∆𝑢2 −𝑊𝑠
+ ෠
+ 𝑔 ∆𝑧 + 𝐹 = (5000010)
𝜌 2 𝑚
When
1. No friction (e.g., smooth pipe)
2. No work (𝑊𝑠 = 0)

Equ. (5000010) reduces to Bernoulli equation (5000011)

∆𝑃 ∆𝑢2
+ + 𝑔 ∆𝑧 = 0 (5000011)
𝜌 2

11/27/2023 Chemical Engineering Principles. Abasaeed 26

Example (5000010) Bernoulli equation
Water flows through the system shown here at a rate of 20 𝐿Τ𝑚𝑖𝑛. Estimate the
pressure required at point (1) if friction losses are negligible.

Solution (5000010)
∆𝑃 ∆𝑢2
+ + 𝑔 ∆𝑧 = 0
𝜌 2
∆𝑧 = 𝑧2 − 𝑧1 = 50 𝑚
∆𝑃 = 𝑃2 − 𝑃1
g= 9.81 𝑚Τ𝑠 2
𝑔𝑐 = 1 (𝑘𝑔. 𝑚)Τ(𝑁. 𝑠 2 )
MB: 𝑚1 = 𝑚2  𝑉1ሶ = 𝑉ሶ2 (𝜌 𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
𝑉ሶ
𝑢 =  𝐴1 = 𝜋 0.252 and 𝐴2 = 𝜋 0.52
𝐴
𝑢1 = 17 𝑚/𝑠 and 𝑢2 = 4.24 𝑚/𝑠
𝑃1 = 4.56 × 102 𝑁Τ𝑚2
𝑃1 = 4.56 𝑏𝑎𝑟

11/27/2023 Chemical Engineering Principles. Abasaeed 27

Example (5000011) Siphoning
Gasoline 𝜌 = 50 𝑙𝑏𝑚 Τ𝑓𝑡 3 is to be siphoned from a tank. The friction loss in the
line is 𝐹ሶ = 0.8 𝑓𝑡. 𝑙𝑏𝑓 Τ𝑙𝑏𝑚 . Estimate how long it will take to siphon 5.00 gal,
neglecting the change in liquid level in the gasoline tank during this process and
assuming that both point (at the liquid surface in the gas tank) and point (in the
tube just prior to the exit) are at 1 atm.
Solution (5000011)
∆𝑃 ∆𝑢2 −𝑊
+ + 𝑔 ∆𝑧 + 𝐹෠ = 𝑠 (5000010)
𝜌 2 𝑚
∆𝑃 = 𝑃2 − 𝑃1 = 0
∆𝑧 = 𝑧2 − 𝑧1 = −2.5 𝑓𝑡
𝐹෠ = 0.8
g= 9.81 𝑚Τ𝑠 2
𝑔𝑐 = 32.174 (𝑙𝑏𝑚 . 𝑓𝑡/𝑠)Τ𝑙𝑏𝑓
𝑢1 = 0 𝑚/𝑠 and ∆𝑢2 = 𝑢22 substitute in (5000010) 
𝑢2 = 10.5 𝑓𝑡/𝑠
 Since  is constant: 𝑉1ሶ = 𝑉ሶ2 = 𝑢2 𝐴 = 3.58 × 10−3 𝑓𝑡 3 Τ𝑠
Convert gal to ft3 
5.0 × 0.1337
𝑡= = 187 𝑠 = 3.1 𝑚𝑖𝑛
3.58 × 10−3
11/27/2023 Chemical Engineering Principles. Abasaeed 28
Example (5000012) Hydraulic Power Generation
Water flows from an elevated reservoir through a conduit to a turbine at a
lower level and out of the turbine through a similar conduit. At a point 100 m
above the turbine the pressure is 207 kPa, and at a point 3 m below the
turbine the pressure is 124 kPa. What must the water flow rate be if the
turbine output is 1.00 MW?
Solution (5000012)
∆𝑃 ∆𝑢2 −𝑊
+ + 𝑔 ∆𝑧 + 𝐹෠ = 𝑠 (5000010)
𝜌 2 𝑚
𝑃2 = 124 𝑘𝑃𝑎
𝑃1 = 207 𝑘𝑃𝑎
𝜌 = 1000 𝑘𝑔Τ𝑚3
∆𝑧 = 𝑧2 − 𝑧1 = −3 − 100 = −103 𝑚
𝑊𝑠 = 1 𝑀𝑊
Assume 𝐹෠ = 0.0 (no data is given for it)
Same pipe size or no pipe dimensions are given  ∆𝑢2 = 0
∆𝑃 −𝑊
Substitute in (5000010) after unifying the units  + 𝑔 ∆𝑧 = 𝑠
𝜌 𝑚
𝑚 = 915 𝑘𝑔/𝑠

11/27/2023 Chemical Engineering Principles. Abasaeed 29

ENERGY BALANCES ON NONREACTIVE SYSTEMS

11/27/2023 Chemical Engineering Principles. Abasaeed 30

In this chapter, enthalpy is calculated from equations (also Table B8 and B9
provide quick values directly). It is crucial to understand how the enthalpy of
different streams is calculated based on the region or point (1-5 previous T-
H figure) in which it lies, the temperature and pressure of the stream.
Remember: the enthalpy reference needs three coordinates (state, T, P).
Energy balances requires setting a reference for H.

Hypothetical Process Path (HPP)

HPP is a hypothetical path taken by the material to go from the initial
condition to the final condition.

For example water from (L,40ºC,0.1)

to (V,150ºC,2)
Note: change ONE coordinate at a
time (i.e., P, then T, then state)
Because most of the data is available
at 1 atm in tables, go for 1 atm first

11/27/2023 Chemical Engineering Principles. Abasaeed 31

Hypothetical Process Path (HPP)
It can be seen from the figure that:
1. Only ONE coordinate is changed at a time.
2. Most of the path is done at 1 atm because the data is usually present in
the literature at 1 atm.
3. The first and the last stage of the HPP is for pressure adjustment
4. If we want to calculate H, we don’t need to use a reference point
because it cancels out.
Calculations of Path Stages
a. Changes in pressure, P, @ constant T
Liquids and Solids:
෡=0
∆𝑈 (600001)
෡ ≈ 𝑉෠ ∆𝑃
∆𝐻 (600002)
Ideal Gases
෡=0
∆𝑈 (600003)
෡=0
∆𝐻 (600004)
If not ideal (𝑇 ≪ 0℃ 𝑜𝑟 𝑃 ≫ 1 𝑎𝑡𝑚), use tables or correlations

11/27/2023 Chemical Engineering Principles. Abasaeed 32

Calculations of Path Stages

b. Changes in temperature, T @ constant pressure

Sensible heat is the heat added to raise or lower the temperature of a substance or
a mixture of substances (regions 1 and 5).
𝑇2
෡ = න 𝐶መ𝑣 𝑑𝑇
∆𝑈 (600005)
𝑇1
where 𝐶መ𝑣 is the specific heat capacity at constant volume. Equ. (600005) is:
A. Exact for ideal gases;
B. A good approximation for liquid and solids;
C. Valid only if 𝑉෠ is constant for real gases
෡
𝜕𝑈
𝐶መ𝑣 𝑇 = (600006)
𝜕𝑇 𝑣
Example (600001)
Calculate the heat required to raise 200 kg of nitrous oxide from 20°C to 150°C in a
constant‐volume vessel. The constant‐volume heat capacity of N2O in this temperature range
is given by the equation
𝑘𝐽
𝐶መ𝑣 = 0.855 + 9.42 × 10−4 𝑇(°𝐶)
𝑘𝑔 . °𝐶

11/27/2023 Chemical Engineering Principles. Abasaeed 33

Solution (600001)
For a closed system with no work, no kinetic or potential energy,
𝑄 = ∆𝑈
From Equ. (60005)  ∆𝑈 ෡ = ‫׬‬150 0.855 + 9.42 × 10−4 𝑇 𝑑𝑇
20
∆𝑈෡ = 121 𝑘𝐽/𝑘𝑔
𝑄 = ∆𝑈 = 𝑚 ∆𝑈 ෡ = 200 × 121 = 24200 𝑘𝐽

Enthalpy calculations
෡
𝜕𝐻
𝐶መ𝑝 𝑇 = (600007)
𝜕𝑇 𝑝
𝑇2
෡ = න 𝐶መ𝑝 𝑑𝑇
∆𝐻 (600008)
𝑇1
where 𝐶መ𝑝 is the specific heat capacity at constant pressure. Equ. (600008) is:
A. Exact for ideal gases (also valid for liquids and solids when ∆𝑃 = 0);
B. Exact only if 𝑃 is constant for real gases
𝑇2
෡ = 𝑉∆𝑃
∆𝐻 ෠ + න 𝐶መ𝑝 𝑑𝑇 (600009)
𝑇1

Equ. (600009) is valid for liquids and solids experiencing changes in pressure.

11/27/2023 Chemical Engineering Principles. Abasaeed 34

Heat capacity formulae
For ideal gases
𝐶መ𝑝 = 𝐶መ𝑣 + 𝑅 (6000010)
For liquids and solids
𝐶መ𝑝 = 𝐶መ𝑣 (6000011)
The heat capacity can either be a constant or a function of temperature (given in Table B2)
𝑘𝐽
𝐶መ𝑝 = 5
𝑚𝑜𝑙. 𝐾
𝐶መ𝑝 = 𝑎 + 𝑏 𝑇 + 𝑐 𝑇 2 + 𝑐 𝑇 3
𝐶መ𝑝 = 𝑎 + 𝑏 𝑇 + 𝑐 𝑇 −2
For example from Table B2 
𝐶መ𝑝,𝑎𝑖𝑟,𝑔 = 28.94 × 10−3 + 0.4147 × 10−5 𝑇 + 0.3191 × 10−8 𝑇 2 − 1.965 × 10−12 𝑇 3 𝑇(°𝐶)
𝐶መ𝑝,𝑐𝑎𝑟𝑏𝑜𝑛,𝑐 = 11.18 × 10−3 + 1.095 × 10−5 𝑇 − 4.891 × 1010 × 10−8 𝑇 2 𝑇(𝐾)

Notes (B2):
1. Table has 2 formulae for 𝐶መ𝑝
𝑘𝐽 𝑘𝐽
2. Units of 𝐶መ𝑝 or 𝐶መ𝑝
𝑚𝑜𝑙.°𝐶 𝑚𝑜𝑙.𝐾
3. Gases are at conditions of ideal gas
4. Column 1: compound name
5. Column 2: compound formula

11/27/2023 Chemical Engineering Principles. Abasaeed 35

Notes (B2) continued:
6. Column 3: molecular weight of the compound
7. Column 4: state of compound (gas, liquid, or solid=crystal)
8. Column 5: which formula to choose
9. Column 6: the units of temperature to be substituted
10. Column 7: the value of “a” multiplied by 103
11. Column 8: the value of “b” multiplied by 105
12. Column 9: the value of “c” multiplied by 108
13. Column 10: the value of “d” multiplied by 1012
14. Column 11: the temperature range in which 𝐶መ𝑝 is valid
Example (600002) Cooling of an Ideal Gas
Assuming ideal‐gas behavior, calculate the heat that must be transferred in each of the
following cases.
a. A stream of nitrogen flowing at a rate of 100 mol/min is heated from 20°C to 100°C.
b. Nitrogen contained in a 5‐liter flask at an initial pressure of 3 bar is cooled from 90°C to
30°C.

Solution (600002)
From Table B2 for nitrogen:
100
(a) 𝑄 = ∆𝐻 = 𝑛 ‫׬‬20 𝐶መ𝑝,𝑁2 ,𝑔 = 0.029 + 0.2199 × 10−5 𝑇 + 0.5723 × 10−8 𝑇 2 − 2.871 × 10−12 𝑇 3 𝑑𝑇
𝑄 = 233 kJ/min

11/27/2023 Chemical Engineering Principles. Abasaeed 36

Solution (600002)
(b) Close system (Equ. 6000010)  𝐶መ𝑣 = 𝐶መ𝑣 − 𝑅 = 𝐶መ𝑝 − 0.008314 (R=0.008314 kJ/(mol.K))
30
𝑄 = ∆𝑈 = 𝑛 ‫׬‬90 𝐶መ𝑝,𝑁2 ,𝑔 = 0.02069 + 0.2199 × 10−5 𝑇 + 0.5723 × 10−8 𝑇 2 − 2.871 × 10−12 𝑇 3 𝑑𝑇

𝑃𝑉 3×5
𝑛= =
𝑅𝑇 0.08314×363
𝑛 = 0.497 𝑚𝑜𝑙
𝑄 = −0.621 kJ

11/27/2023 Chemical Engineering Principles. Abasaeed 37

Example (600003) Evaluation of H Using Heat Capacities and Tabulated Enthalpies
Fifteen kmol/min of air is cooled from 430°C to 100°C. Calculate the required heat removal
rate using (1) heat capacity formulas from Table B.2, (2) specific enthalpies from Table B.8.

Solution (600003)
MB: 𝑛1 = 𝑛2 = 15 𝑘𝑚𝑜𝑙/𝑚𝑖𝑛
No work, kinetic and potential energy 
EB: 𝑄 = 𝑛∆𝐻
(1) From Table B2:
𝐶መ𝑝,𝑎𝑖𝑟,𝑔 = 28.94 × 10−3 + 0.4147 × 10−5 𝑇
+0.3191 × 10−8 𝑇 2 − 1.965 × 10−12 𝑇 3
100
𝑄 = ∆𝐻 = 𝑛 ‫׬‬430 𝐶መ𝑝,𝑎𝑖𝑟,𝑔 𝑑𝑇
𝑄 = −2494.9 kW

(2) From Table B8:

෡1 = 12.18 (Interpolate 400-500C)
𝐻
෡2 = 2.19 (directly @100C)
𝐻
𝑄 = ∆𝐻 = 15 × 2.19 − 12.18 𝑘𝐽/𝑚𝑖𝑛
𝑄 = −2497.5 𝑘𝑊

11/27/2023 Chemical Engineering Principles. Abasaeed 38

Estimation of Heat Capacity
In some cases, one may not be able to find the equations for heat capacity in the literature. A
simple empirical method for estimating Cp is developed by Kopp for liquid and solids (see
Table 10 for values). More accurate Cp estimations are given in Reid, Prausnitz and Poling
book>

Kopp’s rule
For a molecular compound, the heat capacity is
the sum of contributions of each element in the
compound; e.g.,

for solid 𝐶𝑎 𝑂𝐻 2 
𝐶𝑝,𝐶𝑎 𝑂𝐻 2 = 𝐶𝑝,𝐶𝑎 + 2 𝐶𝑝,𝑂 + 2𝐶𝑝,𝐻
𝐶𝑝,𝐶𝑎 𝑂𝐻 2 = 26 + 2 × 17 + 2 × 9.6
𝐶𝑝,𝐶𝑎 𝑂𝐻 2 = 79.2 J/(mol. °𝐶)

for liquid 𝐶𝑎 𝑂𝐻 2 (𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛) 

𝐶𝑝,𝐶𝑎 𝑂𝐻 2 = 𝐶𝑝,𝐶𝑎 + 2 𝐶𝑝,𝑂 + 2𝐶𝑝,𝐻
𝐶𝑝,𝐶𝑎 𝑂𝐻 2 = 33 + 2 × 25 + 2 × 18
𝐶𝑝,𝐶𝑎 𝑂𝐻 2 = 119 J/(mol. °𝐶)

11/27/2023 Chemical Engineering Principles. Abasaeed 39

Heat Capacity of Mixture 𝑪𝒑𝒎𝒊𝒙

𝐶𝑝𝑚𝑖𝑥 = ෍ 𝑦𝑗 𝐶𝑝,𝑗 (6000012)

where yj = mole or mass fraction of component j

Example (600004) Heat Capacity of a Mixture

Calculate the heat required to bring 150 mol/h of a stream containing 60% C2H6 and 40%
C3H8 by volume from 0°C to 400°C. Determine a heat capacity for the mixture as part of the
problem solution

Solution (600004)
𝐶𝑝𝑚𝑖𝑥 = 𝑦𝐸𝑡ℎ 𝐶𝑝,𝐸𝑡ℎ + 𝑦𝑃𝑟𝑜 𝐶𝑝,𝑃𝑟𝑜
From Table B2 get the heat capacities of ethane and propane 
𝐶𝑝𝑚𝑖𝑥 = 𝑦𝐸𝑡ℎ 𝐶𝑝,𝐸𝑡ℎ + 𝑦𝑃𝑟𝑜 𝐶𝑝,𝑃𝑟𝑜
𝐶𝑝𝑚𝑖𝑥 = 0.05683 + 17.39 × 10−5 𝑇 − 8.734 × 10−8 𝑇 2 + 17.05 × 10−12 𝑇 3
Assuming no work, kinetic or potential energy
400
𝑄 = ∆𝐻 = 𝑛 ‫׬‬0 𝐶መ𝑝,𝑚𝑖𝑥 𝑑𝑇
𝑄 = 150 × 34.89 = 5230 𝑘𝐽/ℎ
11/27/2023 Chemical Engineering Principles. Abasaeed 40
Example (600005) Energy Balance on a Gas Preheater
A stream containing 10% CH4 and 90% air by volume is to be heated from 20°C to 300°C.
Calculate the required rate of heat input in kilowatts if the flow rate of the gas is 2000 liters
(STP)/min
Solution (600005)
𝑃 𝑉ሶ 1×2000 𝑚𝑜𝑙
Assume ideal gas  𝑛ሶ = = = 89.3
𝑅𝑇 0.08206×273 𝑚𝑖𝑛

Reference: CH4(g, 20, 1); air(g, 25, 1)

Use B2 for methane and B8 for air
No work, kinetic or potential energy

Inlet-outlet enthalpy table

Input Output

substance ni Hi ni Hi

Methane 8.93 0 8.93 12.07

Air 80.37 -0.144 80.37 8.17

෡ 𝒊)
σ(𝒏𝒊 × 𝑯 -11.57 764.41

𝑄 = ∆𝐻
𝑄 = 764.41 − −11.57
𝑘𝐽
𝑄 = 776 𝑚𝑖𝑛 = 12.93 𝑘𝑊

11/27/2023 Chemical Engineering Principles. Abasaeed 41

Example (600006)
In the figure below what is temperature of the exiting gas? The heat exchanger operates
adiabatically

Solution (600006)
We can use Table B8, however, since the exiting temperature value is required, we will need to do trial
and error.
Adiabatic, no work, kinetic or potential energy 
∆𝐻 = 0
Reference: CO2(g, 500, 1); CO (g, 500, 1); H2O(L, 0.01, 0.00611)
From steam tables: Inlet-outlet enthalpy table
෡𝑤𝑎𝑡𝑒𝑟, 𝑖𝑛 = 105 𝑘𝐽/𝑘𝑔 and 𝐻
𝐻 ෡𝑤𝑎𝑡𝑒𝑟,𝑜𝑢𝑡 = 2747.5 𝑘𝐽/𝑘𝑔 (neglect pressure effects)
𝐶𝑝,𝐶𝑂 = 0.02895 + 0.411 × 10−5 𝑇 + 0.3548 × 10−8 𝑇 2 − 2.22 × 10−12 𝑇 3 Input Output
𝐶𝑝, 𝐶𝑂2 = 0.03611 + 4.223 × 10−5 𝑇 − 2.887 × 10−8 𝑇 2 + 7.464 × 10−12 𝑇 3
substance Ni Hi ni Hi
෡ = ‫𝑝𝐶 𝑇׬‬,𝑖 𝑑𝑡
∆𝐻 𝑖 = 𝐶𝑂 𝑜𝑟 𝐶𝑂2 CO 0.08 mol 0 0.08 mol -6.01
500
CO2 0.92 mol 0 0.92 mol -9.817
෡𝐶𝑂, 𝑖𝑛 = 0.0 𝑘𝐽/𝑚𝑜𝑙 and 𝐻
𝐻 ෡𝐶𝑂 ,𝑖𝑛 = 0.0 𝑘𝐽/𝑚𝑜𝑙 H2O 0.0036 kg 105 0.0036 kg 2747.5
2
෡ is a function of T and solving for T  T=298.73 C
𝐻 ෡ 𝒊)
σ(𝒏𝒊 × 𝑯 0.378 0.378

11/27/2023 Chemical Engineering Principles. Abasaeed 42

Numerical Integration of heat capacity
෡ = ‫𝑇׬‬2 𝐶𝑝 𝑑𝑡 can be evaluated either analytically or numerically (area under the
The integral: ∆𝐻 𝑇1
curve)
Example (600007)
Evaluate the specific enthalpy for a material having 𝐶𝑝 = 5 + 0.2𝑇 − 0.00012𝑇 2 if the
temperature changes from 25 to 200C
Solution (600007)
Analytically
200
෡=න
∆𝐻 𝐶𝑝 𝑑𝑡 = 4493
25
Numerical
ℎ
(a) Trapezoidal rule  ‫= ׬‬ 𝐶𝑝,200 + 𝐶𝑝,25 you need to generate 𝐶𝑝,200 and 𝐶𝑝,25 and direct
2
substitution into 𝐶𝑝 function  T 25 200
200−25
∆𝐻෡= 40.2 + 9.925 = 4386
2 Cp 9.925 40.2
A difference of about 2.4% lower than analytical

(b) Simpson 1/3 rule =={ need to divide into 3 points) 

ℎ T 25 112.5 200
‫=׬‬ 3
𝐶𝑝,200 + 4𝐶𝑝,112.5 + 𝐶𝑝,25
Cp 9.925 25.98 40.2
෡ = 200−112.5 40.2 + 4 × 25.98 + 9.925 = 4493
∆𝐻
3
Generally, the more points one takes, the more closer to analytical solution

11/27/2023 Chemical Engineering Principles. Abasaeed 43

Phase Change
The latent heat is heat added to the same substance to change its phase 𝑆 ↔ 𝐿 ↔ 𝑉 without
raising or lowering the temperature at constant pressure. Heat needed to go from point (2) to
point (4) or vise-versa and it listed in Table B1
Latent heat of vaporization ∆𝐻෡𝑣 (liquid to gas) or latent heat of condensation −∆𝐻 ෡𝑣 (gas to liquid)
Latent heat of melting ∆𝐻෡𝑚 (solid to liquid) or latent heat of freezing −∆𝐻
෡𝑚 (liquid to solid)
Latent heat of sublimation ∆𝐻෡𝑠 (solid to gas)
Example (600008)
At what rate in kW must heat be transferred to a liquid stream of methanol at its normal boiling point to
generate 1500 g/min of saturated methanol vapor?
Solution (600008)
From Table B1 for methanol  ∆𝐻 ෡𝑣 = 35.27 𝑘𝐽/𝑚𝑜𝑙 neglect work, kinetic and potential energies
1500 1
𝑄= × × 35.27 = 27.6 𝑘𝑊
32 60
Example (600009)
100 mol/h of liquid hexane at 25C and 7 bar is vaporized and heated to 300C at the same pressure.
Estimate the rate at which heat must be transferred. In the book pressure is assumed negligible.
Solution (600009)
i) Construct a hypothetical path 
From Table B1 and B2 for hexane 
∆𝐻 ෡𝑣 = 28.85 𝑘𝐽 ; 𝑇𝑏 = 68.74°𝐶; 𝑆𝐺 = 0.659
𝑚𝑜𝑙
𝐶𝑝,ℎ𝑒𝑥.𝑙𝑖𝑞𝑢𝑖𝑑 = 0.2163
𝐶𝑝, 𝐶𝑂2 = 0.13744 + 40.85 × 10−5 𝑇 − 23.92 × 10−8 𝑇 2 + 57.66 × 10−12 𝑇 3
neglect work, kinetic and potential energies

11/27/2023 Chemical Engineering Principles. Abasaeed 44

Solution (600009)
i) Construct a hypothetical path 
From Table B1 and B2 for hexane 
∆𝐻 ෡𝑣 = 28.85 𝑘𝐽 ; 𝑇𝑏 = 68.74°𝐶; 𝑆𝐺 = 0.659
𝑚𝑜𝑙
𝐶𝑝,ℎ𝑒𝑥.𝑙𝑖𝑞𝑢𝑖𝑑 = 0.2163
𝐶𝑝,ℎ𝑒𝑥𝑎𝑛𝑒.𝑣𝑎𝑝𝑜𝑟 = 0.13744 + 40.85 × 10−5 𝑇 − 23.92 × 10−8 𝑇 2 + 57.66 × 10−12 𝑇 3

neglect work, kinetic and potential energies

∆𝐻෡1 = 𝑉෠ ∆𝑃 = 1 86 0.008314 1.01325 − 7 = −0.783 𝑘𝐽
0.659 1000 0.08314 𝑚𝑜𝑙
68.74 𝑘𝐽
෡2 =
∆𝐻 ‫׬‬25 0.2163 𝑑𝑇 = 9.34 𝑚𝑜𝑙
෡3 =
∆𝐻 ෡𝑣 = 28.85 𝑘𝐽
𝐻
𝑚𝑜𝑙
300 𝑘𝐽
෡4 =
∆𝐻 ‫׬‬68.74 𝐶𝑝,ℎ𝑒𝑥𝑎𝑛𝑒.𝑣𝑎𝑝𝑜𝑟 𝑑𝑇 = 51.45 𝑚𝑜𝑙
෡5 = 0 (gas phase)
∆𝐻
∆𝐻෡ = σ𝐻 ෡𝑖 = 89.55 𝑘𝐽
𝑚𝑜𝑙
෡
Q = n ∆ 𝐻 = 100 × 89.55 = 8955 𝑘𝐽/ℎ
Q = 2.49 kW
Estimation of latent heats
When the values of latent heats are not tabulated, one can estimate them by using:
1- Latent heat of vaporization:
Trouton’s rule (30% accuracy)
𝑘𝐽 ≈ 0.088 𝑇𝑏 𝑓𝑜𝑟 𝑛𝑜𝑛𝑝𝑜𝑙𝑎𝑟 𝑙𝑖𝑞𝑢𝑖𝑑𝑠
෡𝑣
∆𝐻 = (6000013)
𝑚𝑜𝑙 ≈ 0.109 𝑇𝑏 𝑓𝑜𝑟 𝑤𝑎𝑡𝑒𝑟; 𝑙𝑜𝑤 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑎𝑙𝑐𝑜ℎ𝑜𝑙
11/27/2023 Chemical Engineering Principles. Abasaeed 45
1- Latent heat of vaporization:

Chen’s equation (2% accuracy)

𝑘𝐽 0.0331 𝑇𝑏 Τ𝑇𝑐 − 0.0327 + 0.0297 𝑙𝑜𝑔10 (𝑃𝑐 )
෡𝑣
∆𝐻 = 𝑇𝑏 (6000014)
𝑚𝑜𝑙 1.07 − 𝑇𝑏 Τ𝑇𝑐
𝑇𝑏 and 𝑇𝑐 are the normal boiling point and critical temperature in kelvin and 𝑃𝑐 is the critical pressure in
atm

One can also use Clausius-Clapeyron equation to estimate the latent of vaporization
෡𝑣
∆𝐻
ln 𝑃 ∗ = − (6000015)
𝑅𝑇
𝑑 ln(𝑃∗ ) ∆𝐻෡𝑣
=− (6000016)
𝑑 1/𝑇 𝑅𝑇

Or Watson’s correlation
0.38
𝑇𝑐 − 𝑇2
෡𝑣 𝑇2 = ∆𝐻
∆𝐻 ෡𝑣 𝑇1 (6000017)
𝑇𝑐 − 𝑇1

2- Latent heat of fusion (melting) :

≈ 0.0092 𝑇𝑚 (𝐾) 𝑓𝑜𝑟 𝑚𝑒𝑡𝑎𝑙𝑙𝑖𝑐 𝑒𝑙𝑒𝑚𝑒𝑛𝑡𝑠
𝑘𝐽
∆𝐻෡𝑚 = ≈ 0.0025 𝑇𝑚 𝐾 𝑓𝑜𝑟 𝑖𝑛𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑𝑠 (6000018)
𝑚𝑜𝑙
≈ 0.0500 𝑇𝑚 𝐾 𝑓𝑜𝑟 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑𝑠

11/27/2023 Chemical Engineering Principles. Abasaeed 46

Example (6000010) Estimation of a Heat of Vaporization
The normal boiling point of methanol is 337.9 K and its critical temperature and pressure are
513.2 K and 78.5 atm. The heat of vaporization at the normal boiling point is 35.3 kJ/mol.

a) Estimate the heat of vaporization at 337.9 K using Trouton's rule and Chen's equation,
and determine the percent error for each estimate.
b) Using the Watson's correlation estimate: the value of the heat of vaporization of methanol
at 200°C using the measured and estimated values at the normal boiling point. Determine
the percent error for each estimate if the measured value is 19.8 kJ/mol.

Solution (6000010)
(a)
Trouton’s rule 
෡𝑣 ≈ 0.109 𝑇𝑏 ≈ 0.109 × 337.9 ≈ 36.83 𝑘𝐽/𝑚𝑜𝑙
∆𝐻
(36.83 − 35.3)
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 4.3%
35.3
Chen’s equation 
𝑘𝐽 0.0331 × 337.9Τ513.2 − 0.0327 + 0.0297 𝑙𝑜𝑔10 (78.5)
෡𝑣
∆𝐻 = 337.9 = 37.25𝑘𝐽/𝑚𝑜𝑙
𝑚𝑜𝑙 1.07 − 337.9Τ513.2
(37.25 − 35.3)
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 5.5%
35.3

11/27/2023 Chemical Engineering Principles. Abasaeed 47

Solution (6000010)
(b) Watson’s correlation 
Measured value @ 473K is∆𝐻 ෡𝑣 473 = 19.8 𝑘𝐽/𝑚𝑜𝑙

Using the actual value 

0.38
513.2 − 473
෡𝑣
∆𝐻 473 = 35.3 = 20.2 𝑘𝐽/𝑚𝑜𝑙
513.4 − 337.9
(20.2 − 19.8)
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 1.88%
19.8

Using Trouton’s value 

0.38
513.2 − 473
෡𝑣
∆𝐻 473 = 36.83 = 21.05 𝑘𝐽/𝑚𝑜𝑙
513.4 − 337.9
(21.05 − 19.8)
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 6.3%
19.8

Using Chen’s value 

0.38
513.2 − 473
෡𝑣
∆𝐻 473 = 37.25 = 21.29 𝑘𝐽/𝑚𝑜𝑙
513.4 − 337.9
(21.29 − 19.8)
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 7.5%
19.8

11/27/2023 Chemical Engineering Principles. Abasaeed 48

Example (6000011) Partial Vaporization of a Mixture
An equimolar liquid mixture of benzene (B) and toluene (T) at 10°C is fed continuously to a
vessel in which the mixture is heated to 50°C. The liquid product is 40.0 mole% B, and the
vapor product is 68.4 mole% B. How much heat must be transferred to the mixture per
g‐mole of feed?

Solution (6000011)
Since no flow rate is given  basis  n1=100 mol/s
MB 
Total  𝑛1 = 𝑛2 + 𝑛3 = 100
Benzene  0.5 𝑛1 = 0.684 𝑛2 + 0.4 𝑛3 = 50
Solving and substituting into the table  𝑛2 = 35.2 and 𝑛3 = 64.8 mol/s
EB 
Assume operation @ 1 atm (no pressure change)
Reference: B(l,10,1) and T(l,10,1) 
10
෡1,𝐵 = න 𝐶𝑝,𝐵,𝑙 𝑑𝑡 = 0
𝐻
10
10
෡1,𝑇 = න 𝐶𝑝,𝑇,𝑙 𝑑𝑡 = 0
𝐻
10
80.1 50
෡2,𝐵 = න
𝐻 ෡𝑣,𝐵,80.1 + න
𝐶𝑝,𝐵,𝑙 𝑑𝑡 + 𝐻 𝐶𝑝,𝐵,𝑣 𝑑𝑡 = 37.52 𝑘𝐽/𝑚𝑜𝑙
10 80.1

11/27/2023 Chemical Engineering Principles. Abasaeed 49

 110.62 50
෡2,𝑇 = න
𝐻 ෡𝑣,𝑇,110.62 + න
𝐶𝑝,𝑇,𝑙 𝑑𝑡 + 𝐻 𝐶𝑝,𝑇,𝑣 𝑑𝑡 = 42.93 𝑘𝐽/𝑚𝑜𝑙
10 110.62
50
෡3,𝐵 = න 𝐶𝑝,𝐵,𝑙 𝑑𝑡 = 5.332 𝑘𝐽/𝑚𝑜𝑙
𝐻
10
50
෡3,𝑇 = න 𝐶𝑝,𝑇,𝑙 𝑑𝑡 = 6.34 𝑘𝐽/𝑚𝑜𝑙
𝐻
10
Enthalpy inlet-outlet table 

Substanc
n_in H_in n_out H_out
e
B(l) 50.00 0.00 25.92 5.33

T(l) 50.00 0.00 38.88 6.34

B(v) 24.43 37.52

T(v) 11.12 42.93

sum 0.00 1778.79

1778.79 − 0
𝑄= = 17.79 𝑘𝐽/𝑚𝑜𝑙
100

11/27/2023 Chemical Engineering Principles. Abasaeed 50

 The Psychrometric (humidity) Chart
The psychrometric chart encompasses many physical properties in one chart; e.g.,
air-water system.

Dry bulb temperature

(x-axis) DA is the
temperature measured
by thermometer or
thermocouple
Absolute humidity or
(moisture content)
(y-axis)
𝐻2 𝑂 𝑣
ha 𝑘𝑔
𝑘𝑔 𝐷𝐴
% Relative humidity;
𝑝𝐻2𝑂
ℎ𝑟 = ∗ × 100
𝑝𝐻2𝑂 (𝑇)
Last curve to the left is
100% Rh and is called
saturation curve

11/27/2023 Chemical Engineering Principles. Abasaeed 51

Due point, Tdp
is temperature at which humid air becomes saturated if it is cooled at constant pressure.
For example, for air at 29C and 20% RH, the dew point temperature is 4C (move
horizontally on the chart, i.e., constant absolute humidity).
𝑚3
Humid volume, 𝑉𝐻 ෠
𝑘𝑔 𝐷𝐴
Humid volume is the total volume occupied by 1 kg of dry air plus the water vapor
accompanying it.
Wet-bulb temperature
A measure of temperature when a water soaked bulb from a wick of a thermometer (after
locating the point, move to left on the parallel negative slope lines until you reach the
100% saturation curve). Fro example for T=30C and 30% relative humidity  wet bulb
temperature is 18C.
Specific enthalpy of saturated air
To determine it, move along the wet bulb temperature to the 100% saturation curve
(extreme left). Fro example for T=30C and 30% relative humidity  the enthalpy is 50
kJ/kg DA
Enthalpy deviation
The almost vertical curves (from top to bottom) give the enthalpy deviation.

11/27/2023 Chemical Engineering Principles. Abasaeed 52

Example (6000012) The Psychrometric Chart
Use the psychrometric chart to estimate (1) the absolute humidity, wet‐bulb
temperature, humid volume, dew point, and specific enthalpy of humid air at 41°C
and 10% relative humidity, and (2) the amount of water in 150 m3 of air at these
conditions.
Solution (6000012)
Locate the point 41°C and 10% relative humidity on the chart 
(1)
𝑘𝑔 𝐻2 𝑂
a) Absolute humidity = 0.0048
1 𝑘𝑔 𝐷𝐴
b) Wet‐bulb temperature = 19C
𝑚3
c) Humid volume = 0.895
1 𝑘𝑔 𝐷𝐴
d) Dew point = 3C
𝑘𝐽
e) Specific enthalpy of humid air =(54.2-0.7) =53.5
1 𝑘𝑔 𝐷𝐴

(2)
1𝑘𝑔 𝐷𝐴 0.0048 𝑘𝑔 𝐻2 𝑂
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = 150 × 𝑚3 ×
0.895 𝑚3 1 𝑘𝑔 𝐷𝐴
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = 0.804 𝑘𝑔 𝐻2 𝑂
11/27/2023 Chemical Engineering Principles. Abasaeed 53
Example (6000013) Material and Energy Balances on an Air Conditioner
Air at 80°F and 80% relative humidity is cooled to 51°F at a constant pressure of 1 atm. Use the
psychrometric chart to calculate the fraction of the water that condenses and the rate at which
heat must be removed to deliver 1000 ft3/min of humid air at the final condition
Solution (6000013)
Basis 1 𝑙𝑏𝑚 of DA
𝑙𝑏 𝐻 𝑂
Feed (1) @ 80°F and ℎ𝑟 = 80%  ℎ𝑎 = 0.018 𝑚 2 ; 𝐻 ෡1 = 38.8 𝐵𝑡𝑢
𝑙𝑏𝑚 𝐷𝐴 𝑙𝑏𝑚 𝐷𝐴
∴ 𝑚1 = 1 × 0.018 = 0.018 𝑙𝑏𝑚 𝐻2 𝑂
𝑙𝑏 𝐻 𝑂
Saturated vapor @ 51°F (2)  ℎ𝑎 = 0.0079 𝑚 2 ; 𝐻 ෡2 = 20.9 𝐵𝑡𝑢
𝑙𝑏𝑚 𝐷𝐴 𝑙𝑏𝑚 𝐷𝐴
∴ 𝑚2 = 1 × 0.0079 = 0.0079 𝑙𝑏𝑚 𝐻2 𝑂
Liquid water (condensate) @ 80°F (3)  𝑚3 = 𝑚1 − 𝑚2 = 0.0101 𝑙𝑏𝑚 𝐻2 𝑂
0.0101
𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑑 𝑤𝑎𝑡𝑒𝑟 = = 0.555
0.018
𝑟𝑒𝑓𝑒𝑟𝑛𝑐𝑒 𝑜𝑓 𝑐ℎ𝑎𝑟𝑡 𝑙, 32℉, 1 𝑡𝑜 𝑙, 51℉, 1) 
𝐵𝑡𝑢
෡3 = 𝐶መ𝑝 ∆𝑇 = 1 × 51 − 32 = 19
𝐻
𝑙𝑏𝑚 𝐷𝐴
𝑄 = ∆𝐻 = 1 × 20.9 + 0.0101 × 19 − 1 × 38.8 = −17.7 𝐵𝑡𝑢
𝑓𝑡 3
෠
Saturated vapor @ 51°F  𝑉𝐻 = 13 
𝑙𝑏𝑚 𝐷𝐴
𝑓𝑡 3
𝑉𝑏𝑎𝑠𝑖𝑠 = 1 𝑙𝑏𝑚 𝐷𝐴 × 13 = 13 𝑓𝑡 3 
𝑙𝑏𝑚 𝐷𝐴
1000
𝑄 = −17.7 𝐵𝑡𝑢 × = −1360 𝐵𝑡𝑢/𝑚𝑖𝑛
13
11/27/2023 Chemical Engineering Principles. Abasaeed 54
 Energy Balances on Reactive Systems

11/27/2023 Chemical Engineering Principles. Abasaeed 55

NOTE
To perform energy balances:
1- write the chemical reaction equation
Balance the equation

Exothermic and Endothermic Reactions

Exothermic Reactions: releases (produces) heat  raises temperature of the system
Endothermic Reactions: needs heat (must be added)  lowers temperature of the system

Heat of Reaction, ∆𝑯 ෡ 𝒓 (𝑻, 𝑷)

The heat of reaction is a function of temperature and pressure. It is amount of heat that is either
released (exothermic reactions) or must be added (endothermic reactions) when stoichiometric
quantities of reactants react to produce products, e.g.,
𝑘𝐽
𝐶𝑎𝐶2 𝑠 + 2𝐻2 𝑂 𝑙 → 𝐶𝑎 𝑂𝐻 2 𝑠 + 𝐶2 𝐻2 ∆𝐻෡𝑟 25°𝐶, 1 𝑎𝑡𝑚 = −125.4 (700001)
𝑚𝑜𝑙
11/27/2023 Chemical Engineering Principles. Abasaeed 56
To avoid confusion related to which material you choose for the mole, use the extent of reaction
(), i.e.,
∆𝐻𝑟 𝑇, 𝑃 = 𝜉 ∆𝐻 ෡𝑟 𝑇, 𝑃 (700002)
𝑛𝑖,𝑜𝑢𝑡 − 𝑛𝑖,𝑖𝑛
𝜉= (700003)
𝜈𝑖
Notes:
1. In Equ. (700002),  is used not n
2. For exothermic reactions ∆𝐻 ෡𝑟 𝑇, 𝑃 is negative; and for endothermic reactions ∆𝐻 ෡𝑟 𝑇, 𝑃 is
positive.
3. At moderate or low pressure ∆𝐻 ෡𝑟 𝑇 is independent of the P and function of T only.
4. The value of the heat of reaction depends on how the chemical reaction equation is written
𝑘𝐽
𝐶𝐻4 𝑔 + 2𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂(𝑙) ∆𝐻෡𝑟 25°𝐶, 1 𝑎𝑡𝑚 = −890.3
𝑚𝑜𝑙
𝑘𝐽
2𝐶𝐻4 𝑔 + 4𝑂2 𝑔 → 2𝑂2 𝑔 + 4𝐻2 𝑂(𝑙) ∆𝐻෡𝑟 25°𝐶, 1 𝑎𝑡𝑚 = −1780.6
𝑚𝑜𝑙
5. The value of the heat of reaction depends on how the state of aggregation (solid, liquid,
gas) of the reactants and products
𝑘𝐽
𝐶𝐻4 𝑔 + 2𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂(𝑙) ∆𝐻෡𝑟 25°𝐶, 1 𝑎𝑡𝑚 = −890.3
𝑚𝑜𝑙
𝑘𝐽
𝐶𝐻4 𝑔 + 2𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂(𝑔) ෡
∆𝐻𝑟 25°𝐶, 1 𝑎𝑡𝑚 = −802.3
𝑚𝑜𝑙
6. The standard heat of reaction is usually determined at 25C and 1 atm denoted by ∆𝐻 ෡𝑟𝑜

11/27/2023 Chemical Engineering Principles. Abasaeed 57

Example (700001) Calculation of Heats of Reaction

1- The standard heat of the combustion of n‐butane vapor is given in the equation below:
13
𝐶4 𝐻10 𝑔 + 𝑂2 𝑔 → 4𝐶𝑂2 𝑔 + 5𝐻2 𝑂 𝑙 ∆𝐻෡𝑟𝑜 = −2878 𝑘𝐽/𝑚𝑜𝑙
2
Calculate the rate of enthalpy change, ∆𝐻ሶ (kJ/s), if 2400 mol/s of CO2 is produced in this reaction
and the reactants and products are all at 25°C.
1- solution (700001)
2400 − 0
𝜉= = 600 𝑚𝑜𝑙/𝑠
4
∆𝐻𝑟 𝑇, 𝑃 = 600 × −2878 = −1726800 𝑘𝐽/𝑠

2-a Calculate the standard heat of the reaction

2 𝐶4 𝐻10 𝑔 + 13 𝑂2 𝑔 → 8 𝐶𝑂2 𝑔 + 10 𝐻2𝑂 𝑙 ∆𝐻෡𝑟𝑜 =? 𝑘𝐽/𝑚𝑜𝑙
2-b Calculate ∆𝐻ሶ (kJ/s) if 2400 mol/s of CO2 is produced in this reaction and the reactants and
products are all at 25°C.
2-a solution (700001)
∆𝐻 ෡𝑟𝑜 = −2 × 2878 = −5756 𝑘𝐽/𝑚𝑜𝑙
2-b solution (700001)
2400 − 0
𝜉= = 300 𝑚𝑜𝑙/𝑠
8
∆𝐻𝑟 𝑇, 𝑃 = 300 × −5756 = −1726800 𝑘𝐽/𝑠

11/27/2023 Chemical Engineering Principles. Abasaeed 58

Example (700001) Continued

3- The heats of vaporization of n‐butane and water at 25°C are 19.2 kJ/mol and 44.0 kJ/mol,
respectively.
(a) Calculate the standard heat of the reaction
13 𝑘𝐽
𝐶4 𝐻10 𝑙 + 𝑂2 𝑔 → 4𝐶𝑂2 𝑔 + 5𝐻2 𝑂 𝑣 ∆𝐻෡𝑟𝑜 =? (𝐴)
2 𝑚𝑜𝑙
(b) Calculate ∆𝐻ሶ (kJ/s) if 2400 mol/s of CO2 is produced in this reaction and the reactants and
products are all at 25°C.

3-a solution (700001)

13 𝑘𝐽
𝐶4 𝐻10 𝑔 + 𝑂 𝑔 → 4𝐶𝑂2 𝑔 + 5𝐻2 𝑂 𝑙 ෡𝑟𝑜 = −2878
∆𝐻 (𝐵)
2 2 𝑚𝑜𝑙
𝑘𝐽
𝐶4 𝐻10 𝑙 → 𝐶4 𝐻10 𝑔 ∆𝐻 ෡𝑟𝑜 = 19.2 (𝐶)
𝑚𝑜𝑙
𝑘𝐽
5 𝐻2𝑂 𝑙 → 5 𝐻2 𝑂 𝑣 ෡𝑟𝑜 = 44.0 × 5
∆𝐻 𝐷
𝑚𝑜𝑙
Add (B)+(C)+(D)  (A)
𝑘𝐽
෡𝑟𝑜 = −2638.8
∆𝐻
𝑚𝑜𝑙
3-b solution (700001)
∆𝐻𝑟 𝑇, 𝑃 = 600 × −2838.8 = −1583280 𝑘𝐽/𝑠

ss
11/27/2023 Chemical Engineering Principles. Abasaeed 59
 ෡𝒓
Calculation of Specific Internal Energy of Reaction, ∆𝑼
To calculate ∆𝑼෡ 𝒓 use Equ.(700004) where only the stoichiometric coefficients of gaseous
components are taken into account
෡ 𝒓 𝑇 = ∆𝑯
∆𝑼 ෡ 𝒓 𝑇 − 𝑅𝑇 ෍ 𝜈𝑖 − ෍ 𝜈𝑖 (700004)
𝑔𝑎𝑠𝑒𝑜𝑢𝑠 𝑔𝑎𝑠𝑒𝑜𝑢𝑠
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Example (700002)
෡ 𝒐𝒓 𝑇 for the following reaction
Calculate ∆𝑼
𝑘𝐽
𝐶2 𝐻4 𝑔 + 2 𝐶𝑙2 𝑔 → 𝐶2 𝐻𝐶𝑙3 𝑙 + 𝐻2 𝑔 + 𝐻𝐶𝑙(𝑔) ෡𝑟𝑜 = −420.8
∆𝐻 (𝐵)
𝑚𝑜𝑙
Solution (700002)
Substitute into (700004) 
𝑘𝐽
෡𝑟𝑜 = −420.8 − 8.314 × 298 × 1 + 1 − 1 + 2
∆𝑈 = −418.32
𝑚𝑜𝑙

Hess’s law
Hess’s rule can be used to calculate the specific heat of reaction of a particular reaction through
algebraic manipulation of a set of chemical reaction equations.

Plz see example (700001) and the following examples for specific heat of reaction calculations.

11/27/2023 Chemical Engineering Principles. Abasaeed 60

Formation Reactions and Heat of Reaction
A formation reaction of a compound is the reaction where the compound is formed from its
elemental constituents in their natural state of occurrence (e.g. O2 NOT O). The standard heat of
formation is obtained from Table B1 (at 25C and 1 atm). For example;
3 𝑘𝐽
𝑁2 𝑔 + 2 𝐻2 𝑔 + 𝑂2 𝑔 → 𝑁𝐻4 𝑁𝑂3 𝑐 ෡𝑟𝑜 = ∆𝐻
∆𝐻 ෡𝑓𝑜 = −365.14 (𝐵)
2 𝑚𝑜𝑙
For elements 
෡𝑓𝑜 = 0
∆𝐻 (700005)
The heat of reaction can be obtained from the algebraic sum of heats of formation of the products
and reactants according to (700006) below
෡𝑟𝑜 = 𝑜
෡𝑓,𝑖 𝑜
෡𝑓,𝑗
∆𝐻 ෍ 𝜈𝑖 ∆𝐻 − ෍ 𝜈𝑗 ∆𝐻 (700006)
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Example (700003) Heat of reaction from heat of formation
Determine ∆𝐻 ෡𝑟𝑜 for the following reaction
𝐶5 𝐻12 𝑙 + 8 𝑂2 𝑔 → 5 𝐶𝑂2 𝑔 + 6 𝐻2 𝑂 𝑙
Solution (700003)
Using data from Table B1 and Equ. (700006) 
𝐶(𝑠) + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 ∆𝐻෡𝑓𝑜 = −393.5 𝑘𝐽/𝑚𝑜𝑙
0.5 𝑂2 (𝑔) + 𝐻2 𝑔 → 𝐻2 𝑂 𝑙 ෡𝑓𝑜 = −285.84 𝑘𝐽/𝑚𝑜𝑙
∆𝐻
5𝐶(𝑠) + 6𝐻2 𝑔 → 𝐶5 𝐻12 𝑙 ෡𝑓𝑜 = −173.0 𝑘𝐽/𝑚𝑜𝑙
∆𝐻

෡𝑟𝑜 = 5 × −393.5 + 6 × (−285.84) − 1 × (−173.0) = −3509.5 𝑘𝐽/𝑚𝑜𝑙

∆𝐻

11/27/2023 Chemical Engineering Principles. Abasaeed 61

Combustion Reactions and Heat of Reaction
A combustion reaction of a compound is the reaction where the compound is burned completely to
form 𝐶𝑂2 𝑔 and 𝐻2 𝑂 𝑙 . The standard heat of combustion is obtained from Table B1 (at 25C and
1 atm). For example;
𝐶5 𝐻12 𝑙 + 8 𝑂2 𝑔 → 5 𝐶𝑂2 𝑔 + 6 𝐻2𝑂 𝑙 ෡𝑟𝑜 = ∆𝐻
∆𝐻 ෡𝑐𝑜 = −3509.5 𝑘𝐽/𝑚𝑜𝑙

The heat of reaction can be obtained from the algebraic sum of standard heats of combustion of
the reactants and products according to (700007) below
෡𝑟𝑜 = 𝑜
෡𝑓,𝑖 𝑜
෡𝑓,𝑗
∆𝐻 ෍ 𝜈𝑖 ∆𝐻 − ෍ 𝜈𝑗 ∆𝐻 (700007)
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

Example (700004) Heat of reaction from heat of combustion

Determine ∆𝐻 ෡𝑟𝑜 for the following reaction
𝐶2 𝐻6 𝑔 → 𝐶2 𝐻4 𝑔 + 𝐻2 𝑔
Solution (700004)
Using data from Table B1 and Equ. (700007) 
𝑜
෡𝑐,𝑒𝑡ℎ𝑎𝑛𝑒
∆𝐻 = −1559.9 𝑘𝐽/𝑚𝑜𝑙
𝑜
෡𝑐,𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒
∆𝐻 = −1411.0 𝑘𝐽/𝑚𝑜𝑙
𝑜
෡𝑐,ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
∆𝐻 = −285.84 𝑘𝐽/𝑚𝑜𝑙

෡𝑟𝑜 = 1 × (−1559.9) − 1 × −1411.0 + 1 × −285.84

∆𝐻 = 136.9 𝑘𝐽/𝑚𝑜𝑙

11/27/2023 Chemical Engineering Principles. Abasaeed 62

Degree of Freedom (DF) Solution (700005)
1. Always perform DF for MB first See the black numbers for ME and blue numbers for
2. You can assume basis provided that (MB+EB) in the Table
2.1 No flow rate is given for the unit
2.2 DF=-1
Degree of Freedom (all must be independent)
If 𝐷𝐹 < −1(i.e., -2, -3….) or a flow rate is given you
MB alone MB+EB
can’t assume basis (for multiple units you may
assume basis but you have to cancel the given flow Unknowns (U)
rates and perform scaling on the flowchart after you 1- Process Variables  11  11
finish) 2- Chemical Reaction Equations  0  0
3. If 𝐷𝐹 = 0 perform MBs
3- Heat load (Q) ---  1
4. If 𝐷𝐹 ≠ 0, perform combined MB and EB to see if
4- Temperature (T) ---  4
it is possible to solve the question.
5. Write EB equation Total U 11 16
6. State the reference Information (I)
7. Do the calculations 1- Material Balance Equations  5  5
Example (700005) Degree of Freedom 2- Flow rates  2  2
Fill in the table  for the following
3- Compositions  3  3
𝑛1 = 100 ; 𝑦1𝐴 = 0.2 ;
𝑦1𝐵 = 0.3; 𝑦1𝐸 = 0.5 ; 4- Relations  1  1

𝑛4𝐷 Τ𝑛4𝐵 = 2.5 ; 𝑛2 = 50 5- Energy Balance Equation ---  1

𝐶
𝑦2 = 0.5 ; 6- Heat load (Q) ---  0
𝑇1 = 298𝐾 ; 𝑇2 = 400𝐾 ; 7- Temperature (T) ---  4
𝑇3 = 370𝐾 ; 𝑇4 = 370𝐾 ;
Total I 11 16
𝐶𝑃𝐴 = 2.7 ; 𝐶𝑃𝐵 = 5
𝐶𝑃𝐶 = 3.4 ; 𝐶𝑃𝐷 = 4 Degree of Freedom = U - I 0 0

11/27/2023 Chemical Engineering Principles. Abasaeed 63

Energy Balances on Reactive Systems
Two methods are used to perform energy balances on reactive systems
1. Heat of Reaction Method
2. Heat of Formation Method
1- Heat of Reaction Method
To perform EBs using this method 
1. Write chemical reaction equation
2. Balance the chemical reaction equation
3. Draw the flowchart with stream numbered
4. Write all components on all streams
5. Perform MBs on the unit
6. Perform EBs on the unit
7. Choose the reference for all materials involved in the reaction equation (state of
aggregation should be as written in chemical reaction equation; the temperature is usually
25C for all components; the pressure is usually 1 atm for all components because the
literature data is usually available at 25C and1 atm for ∆𝐻 ෡𝑓𝑜 or ∆𝐻
෡𝑐𝑜 )
8. For inerts you can choose any reference.
9. Do the calculations to get 𝐻 ෡𝑖 (fill in enthalpy input-output table)
10. Sometimes you may need to solve the MBs and EBs simultaneously
Single reaction  ∆𝐻ሶ = σ𝑜𝑢𝑡 𝑛𝑖 𝐻 ෡𝑖 − σ𝑖𝑛 𝑛𝑖 𝐻 ෡𝑖 + 𝜉∆𝐻 ෡𝑟𝑜 (700008)
𝑜
Multiple reactions  ∆𝐻ሶ = σ𝑜𝑢𝑡 𝑛𝑖 𝐻
෡𝑖 − σ𝑖𝑛 𝑛𝑖 𝐻
෡𝑖 + σ𝑟𝑥𝑛𝑠 𝜉𝑗 ∆𝐻
෡𝑟,𝑗 (700009)
෡𝑖 = ‫𝑇׬‬
No phase or pressure change  𝐻 𝐶መ𝑃,𝑖 𝑑𝑇 (7000010)
𝑇 𝑟𝑒𝑓

11/27/2023 Chemical Engineering Principles. Abasaeed 64

2- Heat of Formation Method
To perform EBs using this method 
1. Write chemical reaction equation
2. Balance the chemical reaction equation
3. Draw the flowchart with stream numbered
4. Write all components on all streams
5. Perform MBs on the unit
6. Perform EBs on the unit
7. Choose the reference for the elements that compose all materials involved in the reaction
equation (state of aggregation should be as elements in their natural state; the temperature
is usually 25C for all components; the pressure is usually 1 atm for all components
෡𝑓𝑜 or ∆𝐻
because the literature data is usually available at 25C and1 atm for ∆𝐻 ෡𝑐𝑜 )
8. For inerts you can choose any reference.
9. Do the calculations to get 𝐻෡𝑖 (fill in enthalpy input-output table)
10. Sometimes you may need to solve the MBs and EBs simultaneously
Single or Multiple reactions 
∆𝐻ሶ = ෍ 𝑛𝑖 𝐻
෡𝑖 − ෍ 𝑛𝑖 𝐻
෡𝑖 (7000011)
𝑜𝑢𝑡 𝑖𝑛
No phase or pressure change 
𝑇
෡𝑖 =
𝐻 ෡𝑓𝑜
∆𝐻 + න 𝐶መ𝑃,𝑖 𝑑𝑇 (7000012)
𝑇𝑟𝑒𝑓

11/27/2023 Chemical Engineering Principles. Abasaeed 65

Example (700006)
Consider the following reaction:
4 𝑁𝐻3 𝑔 + 5𝑂2 𝑔 → 4𝑁𝑂 𝑔 + 6𝐻2 𝑂(𝑣) ∆𝐻෡𝑟𝑜 = −904.7 𝑘𝐽/𝑚𝑜𝑙
100 mol NH3/s and 200 mol O2/s at 25ºC are fed into a reactor in which the ammonia is completely
consumed. The product gas emerges at 300ºC. Assume operation at 1 atm. Calculate the heat
load (Q) using (a) heat of reaction method and (b) heat pf formation method
Solution (700006)
(a) Heat of reaction method
0−100 𝑁𝐻3 𝑁𝐻3
MB: 𝜉 = = 25 𝑚𝑜𝑙/𝑠  𝑛2 = 𝑛1 − 𝜈 𝑁𝐻3 × 𝜉 = 100 − 4 × 25 = 0
−4
𝑂 𝐻 𝑂
𝑛2 2 = 200 − 5 × 25 = 75  𝑛2𝑁𝑂 = 0 + 4 × 25 = 100  𝑛2 2 = 0 − 6/4 × 25 = 150
EB: Q = ∆𝐻ሶ = σ𝑜𝑢𝑡 𝑛𝑖 𝐻 ෡𝑖 − σ𝑖𝑛 𝑛𝑖 𝐻
෡𝑖 + ෡𝑟𝑜
𝜉∆𝐻
Reference: all gases at 25ºC and 1 atm
Input (1) compound Input (1) Output (2)
෡1,𝑁𝐻3 = 0
𝐻
෡1,,𝑂2 = 0
𝐻 𝑛𝑖 ෡𝑖
𝐻 𝑛𝑖 ෡𝑖
𝐻
Output (2)
෡2,𝑂2 = 8.47 (B8) NH3 100 0 0 ---
𝐻
෡2,𝑁𝑜 = ‫׬‬300 𝐶መ𝑃,𝑁𝑂(𝑔) 𝑑𝑇=8.453 (B2)
𝐻 O2 200 0 75 8.47
25
෡
𝐻2,𝐻2𝑂 = 9.57 (B8) NO 0 --- 100 8.453
H2O 0 --- 150 9.57

Q = ∆𝐻ሶ = 2916 − 0 + −22617 = −19701 𝑘𝑊

11/27/2023 Chemical Engineering Principles. Abasaeed 66
Solution (700006) continued
(a) Heat of formation method
MB: Same as before
EB: Q = ∆𝐻ሶ = σ𝑜𝑢𝑡 𝑛𝑖 𝐻෡𝑖 − σ𝑖𝑛 𝑛𝑖 𝐻
෡𝑖
෡𝑓𝑜 + ‫𝐶 𝑇׬‬መ𝑃,𝑖 𝑑𝑇
෡𝑖 = ∆𝐻
𝐻 𝑇𝑟𝑒𝑓
Reference: N2 (g), H2 (g), O2(g) at 25ºC and 1 atm
𝑜
෡𝑓,𝑁𝐻3
∆𝐻 = 46.19
𝑜
compd Input (1) Output (2)
∆𝐻෡𝑓,𝑂2 =0
𝑜
෡𝑓,𝑁𝑂
∆𝐻 = 90.37 ෡𝑖 ෡𝑖
𝑜 𝑛𝑖 𝐻 𝑛𝑖 𝐻
∆𝐻෡𝑓,𝐻2𝑂 = −241.83
Input (1) NH3 100 -46.19 0 ---
෡1,𝑁𝐻3 = −46.19 + 0 = −46.19
𝐻 O2 200 0 75 8.47
෡1,,𝑂2 = 0 + 0 = 0
𝐻 NO 0 --- 100 98.823
H2O 0 --- 150 -232.26
Output (2)
𝐻෡2,𝑂2 = 0 + 8.47 = 8.47 (B8) ෡𝑖 = −4619 ෍ 𝑛𝑖 𝐻
෡𝑖 = −24321.5
෍ 𝑛𝑖 𝐻
𝐻෡2,𝑁𝑜 = 90.37 + ‫׬‬300 𝐶መ𝑃,𝑁𝑂(𝑔) 𝑑𝑇=98.823 (B2) 𝑖𝑛 𝑜𝑢𝑡
25
෡
𝐻2,𝐻2𝑂 = −241.83 + 9.57 = −232.26 (B8)

Q = ∆𝐻ሶ = −24321.5 − −4619 = −19702.5 𝑘𝑊

11/27/2023 Chemical Engineering Principles. Abasaeed 67

Example (700007)
Methane is oxidized with air to form formaldehyde in
a continuous reactor. A competing reaction occurs
𝐶𝐻4 + 𝑂2 → 𝐻𝐶𝐻𝑂 𝑔 + 𝐻2 𝑂 𝑣 (1)
𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂 𝑣 (2)
The figure shows the reactor 
Find the heat load.
Solution (700007)
MB: given
The example is solved by the heat of formation in the compd Input (1,2) Output (3)
book will solve by heat of reaction here
EB: 𝑄 = 𝐻3 − 𝐻1 -𝐻2 + 𝜉1 ∆𝐻 ෡𝑟,1
𝑜 ෡𝑟,2
+ 𝜉2 ∆𝐻 𝑜
𝑛𝑖 ෡𝑖
𝐻 𝑛𝑖 ෡𝑖
𝐻
Reference: all gases, 25C,1 atm
CH4 100 0 60 4.9
Using B1 for standard heat of formation and B2 for CH4
and HCHO and B8 for the rest O2 100 2.235 50 3.758
30−0
𝜉1 = ෡𝑟,1
= 30; ∆𝐻 𝑜
=-241.83-115.9+74.85=-282.9 N2 376 2.187 376 3.655
1
10−0
𝜉2 = = 10; ෡𝑟,2
∆𝐻 𝑜
= 2 −241.83 − 393.5 + 74.85 = −802.3
1 HCHO 0 -- 30 4.75
෡1,𝐶𝐻4 = 0 ; 𝐻
𝐻 ෡2,𝑂2 = 2.235 ; 𝐻
෡2,𝑁2 = 2.187
CO2 0 -- 10 4.75
෡3,𝐶𝐻4 = 4.9 ; 𝐻
𝐻 ෡3,𝑂2 = 3.758 ; 𝐻
෡3,𝑁2 = 3.655
෡3,𝐻𝐶𝐻𝑂 = 4.75 ; 𝐻
𝐻 ෡3,𝐶𝑂2 = 4.75 ; 𝐻
෡3,𝐻2𝑂 = 4.27 H2O 0 -- 50 4.27
Total 𝟏𝟎𝟒𝟓. 𝟖 2259.7
Q = ∆𝐻ሶ = 2259.7 − 1045.8 + 30 −282.9 − 10 −802.3
Q = 15295.6 𝑘𝑊

11/27/2023 Chemical Engineering Principles. Abasaeed 68

Example (700008)
The dehydrogenation of ethanol to acetaldehyde is 𝐶2 𝐻5𝑂𝐻(𝑣) → 𝐶𝐻3 𝐶𝐻𝑂 𝑣 + 𝐻2 𝑔
Is carried out in a continuous adiabatic reactor.
Calculate the product temperature

Solution (700008)
MB: given
The example is solved by the heat of reaction method in the book will solve by heat of formation
here
EB: 𝑄 = 𝐻2 − 𝐻1 = 0
Reference: C(s); H2 (g); O2(g), 25C,1 atm
We use B1 for heats of formation of stream (1) and B2 the heat capacity for all (C2H5OH ; H2, and
CH3CHO) because the exit temperature is needed
෡1,𝐶2𝐻5𝑂𝐻 = −235.31 + 33.79 = −201.52
𝐻
෡2,𝐶2𝐻5𝑂𝐻 = −235.31 + ‫𝑇׬‬2 𝐶መ𝑝,𝐶2𝐻5𝑂𝐻(𝑣) 𝑑𝑇
𝐻 25
𝑇2
෡2,𝐶𝐻3𝐶𝐻𝑂 = −166.2 + ‫𝐶 ׬‬መ𝑝,𝐶𝐻3𝐶𝐻𝑂(𝑣) 𝑑𝑇
𝐻 25
𝑇2
𝐻෡2,𝐻2 = 0 + ‫׬‬25 𝐶መ𝑝,𝐻2 (𝑔) 𝑑𝑇
Integrate, substitute, and solve for T2
Q = ∆𝐻ሶ = 5.19 × 10−10 𝑇24 + 2.813 × 10−6 𝑇23 + 7.492 × 10−3 𝑇22 + 6.673𝑇2 − 1477 = 0

T2 = 181.7C

11/27/2023 Chemical Engineering Principles. Abasaeed 69

Example (700009)
Consider the dehydrogenation of ethanol to
acetaldehyde given in example (700008)
𝐶2 𝐻5 𝑂𝐻(𝑣) → 𝐶𝐻3 𝐶𝐻𝑂 𝑣 + 𝐻2 𝑔 
Calculate the conversion of ethanol
Let E=ethanol, F=formaldehyde, H=hydrogen
Solution (700009) Degree of Freedom (all must be independent)
Degree of Freedom  see table MB alone MB+EB
Unknowns (U)
MB: Atomic method: Input=output 1- Process Variables  5  5
𝑛1𝐸 = 0.9 × 150 = 135 2- Chemical Reaction Equations  1  1
𝑛1𝐹 = 0.1 × 150 = 15 3- Heat load (Q) ---  1

C: 2 × 135 + 2 × 15 = 2 × 𝑛2𝐸 +2 × 𝑛2𝐹 = 300 (A) 4- Temperature (T) ---  2

O: 1 × 135 + 1 × 15 = 1 × 𝑛2𝐸 +1 × 𝑛2𝐹 = 150 (B) Total U 6 9

H: 6 × 135 + 4 × 15 = 6 × 𝑛2𝐸 + 4 × 𝑛2𝐹 + 2 × 𝑛2𝐻 Information (I)

H: 3𝑛2𝐸 + 2𝑛2𝐹 + 𝑛2𝐻 = 435 (C) 1- Material Balance Equations  3  3

2- Flow rates  1  1

Note Equs: (A)=(B) (3 unknowns but 2 Equs)  3- Compositions  1  1

4- Relations  0  0
no solution
5- Energy Balance Equation ---  1
6- Heat load (Q) ---  1
EB: 𝑄 = 𝐻2 − 𝐻1 = 2440 (D)
7- Temperature (T) ---  2
Total I 5 9
Reference: C(s); H2 (g); O2(g), 25C,1 atm
Degree of Freedom = I - U -1 0

11/27/2023 Chemical Engineering Principles. Abasaeed 70

Solution (700009)
We use B1 for heats of formation and B2 for the heat capacity for all (C2H5OH ; H2,
and CH3CHO) for H2 we can, also, use B8 (interpolation)

෡1,𝐶2𝐻5𝑂𝐻 = −235.31 + ‫׬‬300 𝐶መ𝑝,𝐸 (𝑣) 𝑑𝑇

𝐻 25
300
෡1,𝐶𝐻3𝐶𝐻𝑂 = −166.2 + ‫𝐶 ׬‬መ𝑝,𝐹(𝑣) 𝑑𝑇
𝐻 25
෡2,𝐶2𝐻5𝑂𝐻 = −235.31 + ‫׬‬253 𝐶መ𝑝,𝐸(𝑣) 𝑑𝑇
𝐻 25
253
෡2,𝐶𝐻3𝐶𝐻𝑂 = −166.2 +
𝐻 ‫׬‬25 𝐶መ𝑝,𝐹(𝑣) 𝑑𝑇
෡2,𝐻2 = 0 + ‫׬‬253 𝐶መ𝑝,𝐻2 (𝑔) 𝑑𝑇
𝐻 25

Substitute into Equ. (D), and solve (A), (C), and (M) for three unknowns

Q = ∆𝐻ሶ = 𝑛2𝐸 𝐻
෡2,𝐸 + 𝑛2𝐹 𝐻
෡2,𝐹 + 𝑛2𝐻 𝐻
෡2,𝐸 − 135 𝐻෡1,𝐸 − 15 𝐻
෡1,𝐹 = 2440 (M)
𝑛2𝐸 = 92
𝑛2𝐹 = 58
𝑛2𝐻 = 43

Conversion of ethanol = (135-92)/135 = 0.319

11/27/2023 Chemical Engineering Principles. Abasaeed 71
 Fuels and Combustion
In some cases, the intention in performing a reaction is to produce heat energy
rather than products. The reactant is called fuel.
Fuels and Their Properties
Solid fuels: coal, coke, wood, and agricultural waste
Liquid fuels: hydrocarbons, coal tar, ethanol, and shale oils
Gaseous fuels: natural gas, hydrogen, acetylene
Heating Value (HV): the amount of heat released when the fuel is completely
burned to produce CO2 and H2O (= - heat of combustion)
Higher Heating Value (HHV): the amount of heat released when the fuel is
completely burned to produce CO2 and H2O(l)
Lower Heating Value (LHV): the amount of heat released when the fuel is
completely burned to produce CO2 and H2O(v)
𝐻𝐻𝑉 = 𝐿𝐻𝑉 + 𝑛 ∆𝐻 ෡ (7000013)

If the fuel contains a mixture of combustible materials 

𝐻𝑉 = ෍ 𝑥𝑖 𝐻𝑉 𝑖 (7000014)

Where xi is mole or mass fraction depending on units of HV

11/27/2023 Chemical Engineering Principles. Abasaeed 72

For vaporization of H2O
𝐻2 𝑂 𝑙 → 𝐻2 𝑂 𝑣 𝐻෡𝑣° = 44 𝑘𝐽/𝑚𝑜𝑙 (7000015)
Example (7000010)
A natural gas contains 85% methane and 15% ethane by volume. The heats of combustion
of methane and ethane at 25C and 1 atm are given below 
𝐶𝐻4 𝑔 + 2𝑂2 (𝑔) → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂 𝑣 ෡𝑐° = −802 𝑘𝐽/𝑚𝑜𝑙
𝐻
𝐶2 𝐻6 𝑔 + 7/2𝑂2 (𝑔) → 2𝐶𝑂2 𝑔 + 3𝐻2 𝑂 𝑣 𝐻෡𝑐° = −1428 𝑘𝐽/𝑚𝑜𝑙
Calculate HHV (kJ/g) of natural gas
Solution (7000010)
Since the produced H2O is vapor 
Methane: 𝐻 ෡𝑐° = 𝐿𝐻𝑉 = 802 𝑘𝐽/𝑚𝑜𝑙
Ethane: 𝐻෡𝑐° = 𝐿𝐻𝑉 = 1428 𝑘𝐽/𝑚𝑜𝑙
Using Equ. (7000013) and (7000015)
Methane:
𝐶𝐻4 𝑔 + 2𝑂2 (𝑔) → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂 𝑣 ෡𝑐° = −802 𝑘𝐽/𝑚𝑜𝑙
𝐻
2𝐻2 𝑂 𝑣 → 2𝐻2 𝑂 𝑙 ෡𝑣° = −88 𝑘𝐽/𝑚𝑜𝑙
𝐻
𝐻𝐻𝑉𝑚𝑒𝑡ℎ𝑎𝑛𝑒 = − −802 − 2 × 44 = 890 𝑘𝐽/𝑚𝑜𝑙 = 55.625 𝑘𝐽/𝑔
Similarly for ethane  𝐻𝐻𝑉𝑒𝑡ℎ𝑎𝑛𝑒 = − −1428 − 3 × 44 = 1560 𝑘𝐽/𝑚𝑜𝑙 = 52.0 𝑘𝐽/𝑔
Convert volume% to mass %  𝑥𝑚𝑒𝑡ℎ𝑎𝑛𝑒 ≈ 0.75 𝑎𝑛𝑑 𝑥𝑒𝑡ℎ𝑎𝑛𝑒 ≈ 0.25
Equ. (7000014) 
𝐻𝐻𝑉𝑁𝐺 = 0.75 × 55.625 + 0.25 × 52 = 54.7 𝑘𝐽/𝑔

11/27/2023 Chemical Engineering Principles. Abasaeed 73

Adiabatic Flame Temperature (AFT)
AFT is the highest temperature the system operated adiabatically will reach if the reaction is exothermic.
AFT is important to determine, especially in choosing the material of construction of the reactor.
𝑄 = 0 = ∆𝐻ሶ = 𝑛ሶ 𝑓𝑢𝑒𝑙 ∆𝐻
෡𝑐° + ෍ 𝑛ሶ 𝑖 ∆𝐻
෡𝑖 (𝑇𝑎𝑑 − ෍ 𝑛ሶ 𝑖 ∆𝐻
෡𝑖 (𝑇𝑓𝑒𝑒𝑑 (7000016)
𝑜𝑢𝑡 𝑖𝑛
Example (7000011)
Liquid methanol is to be burned with 100% excess air. The engineer designing the furnace must
calculate the highest temperature that the furnace walls will have to withstand so that an appropriate
material of construction can be chosen. Perform this calculation, assuming that the methanol is fed at
25°C and the air enters at 100°C.
Solution (7000011)
From Table B1:
𝐶𝐻3 𝑂𝐻 𝑙 + 1.5 𝑂2 (𝑔) → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂 𝑙 ෡𝑐° = −726.6 𝑘𝐽/𝑚𝑜𝑙
𝐻
Basis: 𝑛1𝐶𝐻3𝑂𝐻 = 100 mol/s (feed methanol)
𝑂2 𝑂2
MB: 𝑛𝑡ℎ𝑒𝑜𝑟 = 100 × 1.5 = 150 ; 𝑛𝑒𝑥𝑐𝑒𝑠𝑠 = 1.0 × 150 = 150
79
∴ 𝑛2𝑂2 = 150 + 150 = 300  𝑛2𝑁2 = × 300 = 1128.6
21
For highest temperature, methanol must burn completely  𝑛ሶ 𝑓𝑢𝑒𝑙 = 𝜉 = 100 
𝑛3𝑂2 = 150 ; 𝑛3𝑁2 = 1128.6 ; 𝑛3𝐶𝑂2 = 100 ; 𝑛3𝐻2𝑂 = 200
Reference: 𝐶𝐻3 𝑂𝐻 𝑙 ; 𝑂2 𝑔 ; 𝐶𝑂2 𝑔 ; 𝐻2 𝑂 𝑙 , 25°C, 1 atm
෡𝑖 : 𝐻
𝐻 ෡1,𝐶𝐻3𝑂𝐻 = 0 ; 𝐻 ෡2,𝑂2 = 2.24 ; 𝐻 ෡3,𝑂2 = ‫𝐶 𝑑𝑎𝑇׬‬መ𝑃,𝑂2 𝑑𝑇 ; 𝐻
෡2,𝑁2 = 2.19 ; 𝐻 ෡3,𝑁2 = ‫𝐶 𝑑𝑎𝑇׬‬መ𝑃,𝑁2 𝑑𝑇 ;
25 25
𝑇𝑎𝑑 𝑇𝑎𝑑
෡3,𝐶𝑂2 = ‫׬‬
𝐻 25
𝐶መ𝑃,𝐶𝑂2 𝑑𝑇 ; 𝐻෡3,𝐻2𝑂(𝑣) = ‫׬‬
25
𝐶መ𝑃,𝐻2𝑂(𝑣) 𝑑𝑇 
EB: Apply Equ. (7000016) and solve the 4th order equation to get
𝑇𝑎𝑑 = 1257°𝐶

11/27/2023 Chemical Engineering Principles. Abasaeed 74

Flammability and Ignition

Note:
The reaction rate doubles when the temperature is raised 10C

Suppose 10%mol methane is burned with air, e.g., 𝐶𝐻4 + 2 𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂. The reaction is heated
from room temperature  with temperature increase, the reaction rate increased and more heat is
generated by the reaction. Turning off the heating source below T=640C will result in drop in
temperature (losses are greater that generation). However, if T>640C the temperature will continue to
rise (generation>losses). T=640C is called the ignition temperature
The value of the ignition temperature depends on many factors including fuel-to-air ratio, total pressure,
and reactor geometry. The lower limit of ignition temperature is called “autoignition temperature”, e.g., at
1 atm and stoichiometric quantities of fuel and air  𝐻2 @400°𝐶 ; 𝐶𝐻4 @540°𝐶
The adiabatic flame temperature (AFT) decreases if the fuel is rich (fuel in excess) or lean (O2 in
excess).

Two values of mole % of fuels in a reaction mixture exists: (1) Lower (lean) flammability limit (LFL) and
(2) Upper (rich) flammability limit (UFL) for which the adiabatic flame temperature equals the ignition
temperature of the mixture. A fuel-air mixture whose % composition falls outside these limits will NOT
ignite or explode even if exposed to a spark. The % composition range falling within (LFL-UFL) is called
explosive range; e.g., for methane-air mixture LFL=5% and UFL=15%, thus, a stoichiometric methane-
air mixture is 9.52% methane  explosive. However, 3% or 20% methane is inexplosive (safe)

 See Table for some values (next slide)

11/27/2023 Chemical Engineering Principles. Abasaeed 75

Example (7000012)
Propane gas and air are to be mixed and fed to a combustion reactor. The combustion is to be initiated
with a gas torch. Determine the minimum and maximum percentages of propane in the feed to the
reactor and the minimum required temperature of the torch flame.

Solution (7000012)
From the table for propane: Flammability Limits, Flash Points, and Autoignition Temperatures for Selected
Species
LFL = 2.2%
HFL = 9.5% Flammability Limits Temperatures (°C)
Tautoignition = 493C Species Lower Upper Flash Point Autoignition
Paraffins
Ttorch > 493C Methane 5.3 15 −222.5 632
Ethane 3 12.5 −130.0 472
Propane 2.2 9.5 −104.4 493
Butane 1.9 8.5 −60.0 408
Olefins
Ethylene 3.1 32 — 490
Propylene 2.4 10.3 −107.8 458
Aromatics
Benzene 1.4 7.1 −11.1 740
Toluene 1.4 6.7 4.4 810
Alcohols
Methanol 7.3 36 12.2 574
Ethanol 4.3 19 12.8 558
Ketones
Acetone 3 13 −17.8 700
Methyl Ethyl Ketone 1.8 10 -4.4 514

11/27/2023 Chemical Engineering Principles. Abasaeed 76