Balance on non-reactive processes

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Energy balances on non-reactive processes

𝑄ሶ = ∆𝐻ሶ = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑛ሶ 𝑖 𝐻
෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑛ሶ 𝑖 𝐻
෡𝑖

Where ; the 𝐻 ෡ 𝑖‘s are the specific enthalpies of inlet and outlet stream
components at their respective process conditions (T, P, and States)
relative to those components at some reference conditions.

In this lecture, it will be presented procedures for evaluating ∆𝐻ሶ or

∆U when the tables of 𝐻 ෡ and 𝑈෡ are not available for all process
species.
Once these calculations have been performed, the energy balance
may be written and solved as before.

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Hypothetical process paths

෡ and ∆𝑈
∆𝐻 ෡ are state properties of a species : that is, their values depend only
on the state of the species, primarily on its temperature and state of aggregation
and, to a lesser extent, on its pressure.
The changes of ∆𝐻 ෡ and ∆𝑈෡ can be classified be following conditions ;

1. Changes in P at constant T and State of aggregation

2. Changes in T at constant P and State of aggregation

3. Phase changes at constant T and P (melting, solidifying,

vaporizing, condensing)

4. Mixing of two liquids or dissolving of gas or solid in a liquid at

constant T and P

5. Chemical reaction at constant T and P

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Hypothetical process paths

For example, calculate ∆𝐻෡ for a process in which solid phenol at 25 oC

and 1 atm is converted to phenol vapor at 300 oC and 3 atm.

A G

B
F

D E

෡ = ∆𝐻
∆𝐻 ෡ 1 + ∆𝐻
෡ 2 + ∆𝐻
෡ 3 + ∆𝐻
෡ 4 + ∆𝐻
෡ 5 + ∆𝐻
෡6

෡ = (𝐻
∆𝐻 ෡𝐵 - 𝐻
෡ 𝐴 ) + (𝐻
෡𝐶 - 𝐻
෡ 𝐵 ) + (𝐻
෡𝐷 - 𝐻
෡ 𝐶 ) + (𝐻
෡𝐸 - 𝐻
෡ 𝐷 ) + (𝐻
෡𝐹 - 𝐻
෡ 𝐸 ) + (𝐻
෡𝐺 - 𝐻
෡𝐹)

෡ = (𝐻
∆𝐻 ෡𝐺 - 𝐻
෡ 𝐴)

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 Changes in phases

Latent Heat is the amount of heat that each component get to change
the phase with no change of their temperature.

Latent heat of melting : ∆𝐻

෡ 𝑚 (T, P )

The difference of enthalpies of component from solid to liquid at

a constant T and P.

Latent heat of evaporation : ∆𝐻

෡ 𝑣 (T, P )

The difference of enthalpies of component from liquid to gas at

a constant T and P.

examples ෡ 𝑣 of water at 25 oC and 760 mmHg is 2442.3 kJ/g

𝐻
෡ 𝑣 of water at 100 oC and 760 mmHg is 2256.9 kJ/g
𝐻

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Changes in phases

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Changes in temperature

Sensible heat
The term sensible heat signifies heat that must be transferred to raise or lower
the temperature of a substance or mixture of substances. The quantity of heat
required to produce a temperature change in a system can be determined
from the appropriate form of the first law of thermodynamics :

Q = ∆U (closed system)
𝑄ሶ = ∆𝐻ሶ (opened system)

𝑊ሶ 𝑠 ; ∆𝐸ሶ k ; ∆𝐸ሶ p neglected

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Changes in temperature

Heat capacity

Heat capacity at constant volume of the substance, denoted by Cv

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Changes in temperature

Heat capacity

Heat capacity at constant pressure, denoted by Cp

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Changes in temperature

Heat Capacity Formulas

Units of heat capacities : J/(mol·K) , Btu/(lbm·oF)

When ; R is the gas constant

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Changes in temperature

Example 11.1 Calculate the heat required to raise 200 kg of nitrous oxide from
20 oC to 150 oC in a constant-volume vessel. The constant-volume
heat capacity of nitrous oxide in this temperature range is given by
the following equation :

Where T is in oC.

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Changes in temperature

Assume ideal gas behavior, calculate the heat that must be

Example 11.2 transferred in each of the following cases.

1. A stream of nitrogen flowing at a rate of 100 mol/min is heated

from 20 oC to 100 oC.
2. Nitrogen contained in a 5 liter flask at an initial pressure of 3
bar is cooled from 90 oC to 30 oC.

From Table B.2, Appendix B, the heat capacity of nitrogen at constant pressure
of 1 atm is following equation ;

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Example 11.2

Then ;

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 Example 11.2 To evaluate ∆U, we need to know Cv

Cp has already given previously and R is following

Then ;

෡;
Calculate ∆𝑼

Calculate n ;

Calculate Q ;

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 Changes in temperature

15 kmol/min of air is cooled from 430 oC to 100 oC. Calculate the

Example 11.3
required heat removal rate using (1) heat capacity formulas from
table B.2 and (2) specific enthalpies from table B.8.

(1) heat capacity formulas from table B.2

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Example 11.3 (2) specific enthalpies from table B.8

Then ;

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Changes in pressure

Changes in pressure at constant temperature

It has been proved experimentally that internal energy is nearly

independent of pressure for solids and liquids at a fixed temperature,
as is specific volume.
Therefore, if the pressure of a solids or liquids changes at
constant temperature, it can be written as ;

෡≈0
∆𝑈

∆𝐻 ෡ + ∆(P𝑉)
෡ = ∆𝑈 ෠ ≈ 𝑉෠ ∆P

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Changes in pressure

Changes in pressure at constant temperature

Both 𝑈෡ and 𝐻 ෡ are independent of pressure for ideal gas.

Consequently, you may generally assume ∆𝑈 ෡ ≈ 0 and ∆𝐻෡ ≈ 0 for a gas
undergoing an isothermal pressure change unless gases at
temperatures well below 0 oC or well above 1 atm are involved.

For ideal gas ෡≈0

∆𝑈

෡≈0
∆𝐻

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 Vaporization and Heating

Example 11.4 100 gmol/h of liquid n-hexane at 25 oC and 7 bar is vaporized and
heated to 300 oC at constant pressure. Avoid the effect of pressure on
enthalpy, estimate the rate at which heat must be supplied.

neglected
For Opened System
𝑄ሶ - 𝑊ሶ 𝑠 = ∆𝐻ሶ + ∆𝐸ሶ k + ∆𝐸ሶ p

𝑄ሶ = ∆𝐻ሶ = 𝑛∆ ෡
ሶ 𝐻

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Example 11.4

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Example 11.4

Over All Process ;

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Procedure of energy balance calculations

1. Perform all required material balance calculations.

2. Write the appropriate form of the energy balance (closed or opened

system) and cut off any terms that are negligible or zero for the given
process system.

3. Choose a reference state (phase), temperature, and pressure for

each species involved in the process.

4. For a closed constant-volume system, construct a table with columns

for initial and final amounts of each species (mi or ni) and specific
෡ 𝑖)2. For an
internal energies relative to the chosen reference states (𝑈
opened system, construct a table with columns for inlet and outlet
stream component flow rates ( 𝑚ሶ 𝑖 or 𝑛ሶ 𝑖 ) and specific enthalpies
෡ 𝑖).
relative to the chosen reference state (𝐻

෡ 𝑖 or 𝐻
5. Calculate all required values of 𝑈 ෡ 𝑖 and insert the values in the
appropriate places in the table.

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Procedure of energy balance calculations

6. Calculate

Closed System ∆𝑈ሶ = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑚ሶ 𝑖𝑈

෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑚ሶ 𝑖 𝑈
෡ 𝑖 or ∆𝑈ሶ = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑛ሶ 𝑖𝑈
෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑛ሶ 𝑖𝑈
෡𝑖

Opened System ∆𝐻ሶ = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑚ሶ 𝑖𝐻

෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑚ሶ 𝑖𝐻
෡ 𝑖 or ∆𝐻ሶ = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑛ሶ 𝑖𝐻
෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑛ሶ 𝑖 𝐻
෡𝑖

7. Calculate any 𝑊ሶ 𝑠 , ∆𝐸ሶ k ,and ∆𝐸ሶ p terms that you have not dropped from energy balance.

8. Solve the energy balance for whichever variable is unknown (often Q or 𝑄ሶ ).

Closed System Q - 𝑊= ∆𝐻+ ∆𝐸 k + ∆𝐸 p

Opened System 𝑄ሶ - 𝑊ሶ 𝑠 = ∆𝐻ሶ + ∆𝐸ሶ k + ∆𝐸ሶ p

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 Energy balance on a condenser

Acetone, denoted as Ac, is partially condensed out of a gas

Example 11.5
stream containing 66.9 mole% acetone vapor and the balance
nitrogen. Process specifications and material balance calculations
lead to the flowchart shown below ;

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Example 11.5 neglected
For Opened System
𝑄ሶ - 𝑊ሶ 𝑠 = ∆𝐻ሶ + ∆𝐸ሶ k + ∆𝐸ሶ p

𝑄ሶ = ∆𝐻ሶ = 𝑛∆ ෡
ሶ 𝐻

𝑄ሶ = ∆𝐻ሶ = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑛ሶ 𝑖𝐻
෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑛ሶ 𝑖𝐻
෡𝑖

Choose reference states for acetone and nitrogen

From table B.8 ;

N2 (g, 25 oC, 1 atm)
Ac (l, 20 oC, 5 atm)

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Example 11.5 ෡
Calculate the unknown 𝐻

From table B.2 ; Cp(T) must be known, where T is in oC.

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Example 11.5

Then ;

෡ 1 = (0.0297 + 4.68 + 30.2 +0.753) kJ/mol

𝐻

= 35.7 kJ/mol

෡2 , 𝐻
Proceeding in the similar manner, we then obtain the values for 𝐻 ෡ 3 , and 𝐻
෡4
shown in the following table ;

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Example 11.5 Calculate for ∆𝑯ሶ ;

∆𝐻ሶ = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑛ሶ 𝑖𝐻
෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑛ሶ 𝑖𝐻
෡𝑖

Since, there are zero of work, kinetic energy, and potential energy terms.

Then ; 𝑄ሶ = ∆𝐻ሶ

= − 2320 kJ/s

= − 2320 kW

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 Energy balance on a gas preheater

Example 11.6 A stream containing 10% methane and 90% air by volume is to be
heated from 20 oC to 300 oC. Calculate the required rate of heat input
in “kW” if the flow rate of the gas is 2,000 L at STP/min.

At STP imply to molar flow rate, not T and P

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Example 11.6 For Opened System 𝑄ሶ - 𝑊ሶ 𝑠 = ∆𝐻ሶ + ∆𝐸ሶ k + ∆𝐸ሶ p

𝑄ሶ = ∆𝐻ሶ = 𝑛∆ ෡
ሶ 𝐻
Choose reference states

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Example 11.6 The enthalpies of air at the inlet and outlet conditions relative to air
at the reference state (𝐻 ෡ 2 and 𝐻 ෡ 3, respectively) are determined
from Table B.8 as shown following;

Finally, Energy balance is

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 Energy balance on a waste heat boiler

Example 11.7 A gas stream containing 8.0 mole% CO and 92.0 mole% CO2 at
500 oC is fed to a waste heat boiler. The hot gas flows over the
outside of the tubes. Liquid water at 25 oC is fed to the boiler in a
ratio 0.200 mol feedwater/mol hot gas and flow inside the tubes.
Heat is transferred from the hot gas through the tube walls to the
water, causing the gas to cool and the water to heat to its boiling
point and evaporate to form saturated steam at 5.0 bar. The
flowchart for an assume basis of 1.00 mol feed gas is shown below.

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Example 11.7 Energy Balance ;

෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑛ሶ 𝑖𝐻
∆𝐻 = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑛ሶ 𝑖𝐻 ෡𝑖 = 0

Choose reference

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Example 11.7 From table B.2 ; Cp(T) must be known, where T is in oC.

෡ 3 and 𝐻
Substituting the resulting expressions and the values of 𝐻 ෡ 4 in to the
energy balance (∆𝐻 = 0) then the equation has shown following ;

The solution is therefore T ≈ 299

oC
Principles and Calculations in Petrochemical 34
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Energy balance on a vaporization of a mixture

An equimolar liquid mixture of benzene, denoted as B, and toluene,

Example 11.8
denoted as T, at 10 oC is fed continuously to a vessel in which the
mixture is heated to 50 oC. 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?

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Example 11.8 Mass balance ;

Energy balance ; 𝑄= ∆𝐻

Choose reference inlet and outlet

Principles and Calculations in Petrochemical 36

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Example 11.8 ෡𝒊 ;
Calculate for ∆𝑯

Energy balance ; ෡ 𝑖 − σ𝑖𝑛𝑙𝑒𝑡 𝑛𝑖𝐻

𝑄 = ∆𝐻 = σ𝑜𝑢𝑡𝑙𝑒𝑡 𝑛𝑖𝐻 ෡𝑖

𝑄 = 17.7 kJ

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