Steady State Mass Balance

(Single and Multi-Phase Systems)

A/Prof. Lanry Yung

Department of Chemical and Biomolecular Engineering

National University of Singapore

© Copyright National University of Singapore. All Rights Reserved.

1
Overview for Steady-State Mass/Material Balance

1.1 Process classification

1.2 Mass Balance Week 1
1.3 Balance calculations
1.4 Single-unit processes
1.5 Multiple-unit processes Week 2
1.6 Recycle and bypass
1.7 Chemical Reaction Stoichiometry
1.8 Balances on reactive processes Week 3
1.9 Combustion reactions
1.10 Single-phase systems
Week 4
1.11 Multiphase systems

2
Overview for This Session

1.10 Single Phase Systems

– Ideal gases
– Non-ideal gases

1.11 Multiphase systems

– Single-component phase equilibrium
– Gibbs Phase rule
– Gas-liquid systems

3
1.10 Single Phase Systems
Physical properties
 PVT, vapor pressure, solubility, density, heat capacity, thermal conductivity, etc.

Physical property data resources:

• Perry’s Chemical Engineers’ Handbook (8th Ed)
• CRC Handbook of Chemistry and Physics (9th Ed)
• NIST Chemistry WebBook (https://webbook.nist.gov/chemistry/)

Why need to know the physical properties?

4
Ideal Gases
Ideal-Gas Equation of State (EoS)
𝑃𝑃𝑃𝑃 = 𝑛𝑛𝑛𝑛𝑛𝑛 or 𝑃𝑃𝑉𝑉̇ = 𝑛𝑛𝑅𝑅𝑅𝑅
̇ or 𝑃𝑃𝑉𝑉� = 𝑅𝑅𝑅𝑅
where
𝑃𝑃 = absolute pressure of gas
𝑉𝑉 𝑜𝑜𝑜𝑜 𝑉𝑉̇ = volume (volumetric flow rate) of the gas
𝑛𝑛 𝑜𝑜𝑜𝑜 𝑛𝑛̇ = number of moles (molar flow rate) of the gas
𝑉𝑉� = molar volume of the gas
𝑅𝑅 = gas constant (depends on units of P, V, n and T used) with units of (pressure x
volume)/(mole x temperature)
𝑇𝑇 = absolute temperature of the gas
Valid generally at temperatures above 0℃ and pressures below 10 atm

5
Standard Temperature and Pressure

𝑃𝑃𝑉𝑉� = 𝑅𝑅𝑅𝑅

At standard temperature 𝑇𝑇𝑠𝑠 = 273K and 𝑃𝑃𝑠𝑠 = 1atm,

𝑅𝑅𝑇𝑇𝑠𝑠 0.08206 × 273 𝐿𝐿
𝑉𝑉�𝑠𝑠 = = = 22.4
𝑃𝑃𝑠𝑠 1 𝑚𝑚𝑚𝑚𝑚𝑚

You may use:

𝑃𝑃𝑉𝑉 𝑇𝑇 𝑃𝑃𝑉𝑉̇ 𝑇𝑇
= 𝑛𝑛 𝑜𝑜𝑜𝑜 = 𝑛𝑛̇
𝑃𝑃𝑠𝑠 𝑉𝑉�𝑠𝑠 𝑇𝑇𝑠𝑠 𝑃𝑃𝑠𝑠 𝑉𝑉�𝑠𝑠 𝑇𝑇𝑠𝑠

6
Ideal Gas Mixture & Partial Pressure
Partial pressure of a component in an ideal gas mixture is the mole fraction of
that component times the total pressure.
𝑝𝑝𝐴𝐴 = 𝑦𝑦𝐴𝐴 𝑃𝑃
𝑦𝑦𝐴𝐴 + 𝑦𝑦𝐵𝐵 + ⋯ = 1
𝑝𝑝𝐴𝐴 + 𝑝𝑝𝐵𝐵 + ⋯ = 𝑦𝑦𝐴𝐴 + 𝑦𝑦𝐵𝐵 + ⋯ 𝑃𝑃 = 𝑃𝑃

Similarly, for component volume fraction:

𝑣𝑣𝐴𝐴 = 𝑦𝑦𝐴𝐴 𝑉𝑉
𝑦𝑦𝐴𝐴 + 𝑦𝑦𝐵𝐵 + ⋯ = 1
𝑣𝑣𝐴𝐴 + 𝑣𝑣𝐵𝐵 + ⋯ = 𝑦𝑦𝐴𝐴 + 𝑦𝑦𝐵𝐵 + ⋯ 𝑉𝑉 = 𝑉𝑉

7
Non-Ideal Gases
Critical Temperature and Pressure
The highest temperature at which a species can co-exist in 2 phases (liquid and
vapor) is the critical temperature of that species, 𝑇𝑇𝑐𝑐 and the corresponding
pressure is the critical pressure, 𝑃𝑃𝑐𝑐 . A substance at its 𝑇𝑇𝑐𝑐 and 𝑃𝑃𝑐𝑐 is said to be at is
critical state. Substances at temperatures above 𝑇𝑇𝑐𝑐 and pressures above 𝑃𝑃𝑐𝑐 are
referred to as supercritical fluids.

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Other Equations of State
Virial Equations of State:

𝑃𝑃𝑉𝑉� 𝐵𝐵 𝐶𝐶 𝐷𝐷
=1+ + 2+ 3+⋯
𝑅𝑅𝑅𝑅 𝑉𝑉� 𝑉𝑉� 𝑉𝑉�

• Coefficients B, C, D are functions of temperature.

• Critical temperature 𝑇𝑇𝑐𝑐 used to calculate reduced temperature 𝑇𝑇𝑟𝑟 used to
describe the coefficients B, C, D, …
𝑇𝑇
𝑇𝑇𝑟𝑟 =
𝑇𝑇𝑐𝑐

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Cubic Equations of State:
Van der Waals Equation of State, Redlich-Kwong, Soave-Redlich-Kwong (SRK) and
Peng Robinson (PR), etc.
𝑇𝑇𝑐𝑐 and 𝑃𝑃𝑐𝑐 used in estimation of parameters in the equations.

Compressibility – factor Equation of State

𝑃𝑃𝑉𝑉�
𝑧𝑧 =
𝑅𝑅𝑅𝑅
For ideal gases, z = 1
𝑇𝑇𝑐𝑐 and 𝑃𝑃𝑐𝑐 used in estimation of z

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1.11 Multiphase Systems
• Many chemical processes involve operations where species/components are
transferred from one phase (gas, liquid, solid) into another.

• When a species transfers from one phase to another, the transfer rate gradually
decreases until the 2nd phase is saturated;
• When the concentrations of all species in each phase do not change with time, the
phases are in phase equilibrium.

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Single Component Phase Equilibrium
A phase diagram of a pure species is a plot of one system variable against another
that shows the conditions at which the species exists as a solid, a liquid and a gas.

P-T phase diagram of water

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Single Component Phase Equilibrium
1. On the vapor-liquid equilibrium curve (A-B),
P is the vapor pressure at T, the T is the boiling
point at P.

2. At P = 1 atm, the T is the normal boiling

point of the species.

3. If (T, P) falls on the solid-liquid equilibrium curve (A-D), T is the melting point or
freezing point at P.

13
Single Component Phase Equilibrium
4. If (T,P) falls on the solid-vapor equilibrium
curve (A-C), P is the vapor pressure of the
solid at T, and T is the sublimation point at P.

5. The point (T,P) at which solid, liquid and

vapor phases can coexist is called the triple
point (POINT A).

6. The vapor-liquid equilibrium curve terminates at the critical temperature and

critical pressure (Tc and Pc) (POINT B). Above and to the right of the critical point,
two separate phases never coexist.

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Estimation of Vapor Pressures
• The volatility of a species is the tendency of the species to transfer from the
liquid (or solid) phase to vapor phase.
• The vapor pressure of a species quantitatively measures its volatility (the
higher the vapor pressure at a given temperature, the greater the volatility of
the species at that temperature).

Clapeyron Equation:
𝑑𝑑𝑝𝑝∗ ∆𝐻𝐻� 𝑉𝑉
= �𝑔𝑔 −𝑉𝑉�𝑙𝑙 )
𝑑𝑑𝑑𝑑 𝑇𝑇(𝑉𝑉
𝑉𝑉�𝑔𝑔 and 𝑉𝑉�𝑙𝑙 are the molar volumes (volume/mole) of gas (vapor) and liquid, respectively
∆𝐻𝐻 �𝑉𝑉 is the latent heat of vaporization (energy required to vaporize one mole of the liquid)

15
Estimation of Vapor Pressures
𝑑𝑑𝑝𝑝∗ ∆𝐻𝐻� 𝑉𝑉
= �𝑔𝑔 −𝑉𝑉�𝑙𝑙 )
𝑑𝑑𝑑𝑑 𝑇𝑇(𝑉𝑉
Except at extremely high pressure, specific volume of liquid is negligible compared
with that of the vapor (i.e. 𝑉𝑉�𝑔𝑔 − 𝑉𝑉�𝑙𝑙 ≈ 𝑉𝑉�𝑔𝑔 ). Applying ideal-gas equation, 𝑉𝑉�𝑔𝑔 = 𝑅𝑅𝑅𝑅�𝑝𝑝∗
to yield:

Clausius-Clapeyron equation:
�𝑉𝑉
∆𝐻𝐻
𝑙𝑙𝑙𝑙 = −𝑝𝑝∗ + 𝐵𝐵
𝑅𝑅𝑅𝑅
𝐵𝐵 is a constant that varies from one species to another.

16
Estimation of Vapor Pressures
A relatively simple empirical equation that correlates vapor pressure-temperature
data extremely well is the Antoine equation:
∗
𝐵𝐵
𝑙𝑙𝑙𝑙g10 𝑝𝑝 = 𝐴𝐴 −
𝑇𝑇 + 𝐶𝐶
(try to rearrange to make T the subject, i.e. boiling point temperature 𝑇𝑇𝑏𝑏 at
specified pressure, P)

Values of A, B and C can be found in the textbook appendix (as well as handbooks).

*Note the valid temperature ranges and do not extrapolate for ranges well outside the
recommended range as it may lead to errors.

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18
The Gibbs Phase Rule
• Extensive variables: dependent on the size of the system, such as volume and
mass.
• Intensive variables: independent on the size, e.g., density, temperature,
pressure, specific volume, mass and mole fractions of individual components in
each phase.
• Degrees of freedom: the number of intensive variables that can be specified
independently for a system at equilibrium.

19
The Gibbs Phase Rule

Gibbs phase rule:

𝐷𝐷𝐷𝐷 = 2 + 𝑐𝑐 − Π − 𝑟𝑟
where
𝐷𝐷𝐷𝐷 is the degree of freedom
𝑐𝑐 is the number of independent chemical species
Π is the number of phases in a system at equilibrium
𝑟𝑟 is the independent chemical reactions among the species

20
Example
Determine the degrees of freedom for each systems at equilibrium below. Specify a feasible set of
independent variables for each system.
1. Pure liquid water
• One phase (Π = 1), one component (c= 1) → DF= 2 + 1 − 1 = 2;
• 2 intensive variables must be specified to fix the state of the system, e.g., T and P.

2. A mixture of liquid, solid and vapor water

• Three phases (Π = 3), one component (c= 1) → DF= 2 + 1 − 3 = 0;
• No further information about the system is needed and all intensive variables are fixed (triple
point).

3. A vapor-liquid mixture of acetone and methyl ethyl ketone

• Two phases (Π = 2), two component (c= 2) → DF= 2 + 2 − 2 = 2;
• Two intensive variables must be specified to fix the state of the system, e.g., specifying T and P
fixes the acetone and MEK mole fractions in both the vapor and liquid phases.

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Gas-Liquid Systems: One Condensable Component

Systems containing several components, of which only one is capable of existing

as a liquid at the process condition (e.g. water in air).
• Transfer of liquid into the gas phase
– Evaporation, humidification
• Transfer of condensable species from gas to the liquid phase
– Condensation, dehumidification

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Raoult’s Law: Single Condensable Species

Refers to the partial

Saturated vapor pressure
pressure of component 𝑝𝑝𝑖𝑖 = 𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑝𝑝𝑖𝑖∗ 𝑇𝑇 of component i at given T
i in the vapor

Total pressure of the vapor

If a gas at temperature T and pressure P contains a saturated vapor whose mole

fraction is yi (mol vapor/mol total gas), and if this vapor is the only species that
would condense if the temperature is slightly lowered, then the partial pressure of
the vapor in the gas equals the pure-component vapor pressure 𝑝𝑝𝑖𝑖∗ T at the
system pressure.

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Example
Air and liquid water are contained at equilibrium in a closed chamber at 75℃ and
760 mm Hg. Calculate the molar composition of the gas phase.

𝑝𝑝𝑖𝑖 = 𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑝𝑝𝑖𝑖∗ 𝑇𝑇

At Temperature, T = 75℃;
Air
Vapor pressure of water 𝑝𝑝𝑖𝑖∗ = 289.1 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 (Appendix B.3)

𝑦𝑦𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝑃𝑃 = 289.1𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
Water 289.1
Given that P = 760 mmHg, 𝑦𝑦𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 = = 𝟎𝟎. 𝟑𝟑𝟑𝟑𝟑𝟑 𝑚𝑚𝑚𝑚𝑚𝑚 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤/𝑚𝑚𝑚𝑚𝑚𝑚
760
𝑦𝑦𝑑𝑑𝑑𝑑𝑑𝑑 𝑎𝑎𝑎𝑎𝑎𝑎 = 1 − 𝑦𝑦𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 = 𝟎𝟎. 𝟔𝟔𝟔𝟔𝟔𝟔 𝑚𝑚𝑚𝑚𝑚𝑚 𝑑𝑑𝑑𝑑𝑑𝑑 𝑎𝑎𝑎𝑎𝑎𝑎/𝑚𝑚𝑚𝑚𝑚𝑚

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Gas-Liquid Systems: One Condensable Component
Note that:
1. A gas in equilibrium with a liquid must be saturated with the volatile
component of that liquid.
2. 𝑝𝑝𝑖𝑖 cannot exceed 𝑝𝑝𝑖𝑖∗ 𝑇𝑇 ; increasing 𝑝𝑝𝑖𝑖 leads to condensation.
3. If 𝑝𝑝𝑖𝑖 < 𝑝𝑝𝑖𝑖∗ 𝑇𝑇 , the vapor is superheated.
4. To condense superheated vapor, one can decrease T at constant P until it
reaches the dew point temperature (or dew point).
𝑝𝑝𝑖𝑖 = 𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑝𝑝𝑖𝑖∗ 𝑇𝑇𝑑𝑑𝑑𝑑

The difference between the temperature T and the dew point 𝑇𝑇𝑑𝑑𝑑𝑑 of a gas is called
the degree of superheat.

25
Example
A stream of air at 100℃ and 5260 mmHg contains 10.0 mol% water vapor.
1. Calculate the dew point temperature and degree of superheat of the air at constant
pressure.
2. Calculate the percentage of the water vapor that condenses and the final
composition of the gas phase if the air is cooled to 80℃ at constant pressure.

26
2. Calculate the percentage of the water vapor that condenses and the final
composition of the gas phase if the air is cooled to 80℃ at constant pressure.

27
Multicomponent Gas-Liquid Systems

Gas-liquid systems with several components in each phase

T and P • Chemical Reactions
A, B, C, … • Distillation
• Absorption
𝑦𝑦𝐴𝐴 , 𝑦𝑦𝐵𝐵 , 𝑦𝑦𝐶𝐶 …
The distribution of each component in each phase is
dependent on its volatility and its content.

𝑥𝑥𝐴𝐴 , 𝑥𝑥𝐵𝐵 , 𝑥𝑥𝐶𝐶 … The Gibbs phase rule applies on the number of intensive
system variables that may be specified.
E.g. At given T and P, the fraction of each component is fixed
for a two-component system.
𝐷𝐷𝐷𝐷 = 2 + 𝑐𝑐 − Π − 𝑟𝑟 = 2 + 2 − 2 − 0 = 𝟐𝟐

28
Multicomponent Gas-Liquid Systems
Vapor-liquid equilibrium data
• Best way to evaluate compositions is from tabulated data (try Perry’s Chemical
Engineer’s Handbook).
– E.g. Partial pressure of vapors over various liquid solutions

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Multicomponent Gas-Liquid Systems
2 useful concepts:
Raoult’s Law
𝑝𝑝𝑖𝑖 ≡ 𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑥𝑥𝑖𝑖 𝑝𝑝𝑖𝑖∗ (𝑇𝑇)
Compare with single condensable species??

Henry’s Law (For solutions where 𝑥𝑥𝑖𝑖 ≈ 0, i.e. dilute solutions of species i)
𝑝𝑝𝑖𝑖 ≡ 𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑥𝑥𝑖𝑖 𝐻𝐻𝑖𝑖 (𝑇𝑇)
• 𝑯𝑯𝒊𝒊 (𝑻𝑻) is the Henry’s law constant for species i in specific solvent.
• Henry’s Law constants (for several gases in water) can be found in Perry’s
Chemical Engineer’s Handbook.
• Typically applied to solutions of non-condensable gases.

30
Example
Use either Raoult’s law or Henry’s law (whichever appropriate) to solve the following
problems.
1. A gas containing 1.0 mol% ethane is in contact with water at 25.0℃, 20.0 atm.
Estimate the mole fraction of dissolved ethane.
2. An equimolar liquid mixture of benzene (B) and toluene (T) is in equilibrium with its
vapor at 30.0℃. What is the system pressure (P) and composition of the vapor?

31
2. An equimolar liquid mixture of benzene (B) and toluene (T) is in equilibrium with its
vapor at 30.0℃. What is the system pressure (P) and composition of the vapor?

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Graphical Representation of Vapor-Liquid Equilibrium (VLE)

Suppose we want to determine the bubble point temperature (Tbp) of a solution

of 2 components, for example – benzene (more volatile) and toluene, at fixed
pressure, at different values of liquid-phase mole fraction. What would be the
quickest way?

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Graphical Representation of VLE
Benzene – Toluene binary mixture system
Txy diagram Pxy diagram

P = 1 atm T = 100℃

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Example: Calculations using Txy Diagrams - 1
Using the Txy diagram, estimate the bubble-point temperature and equilibrium vapor
composition associated with a 40 mol% benzene – 60 mol% toluene liquid mixture at 1 atm.
If the mixture is steadily vaporized until the remaining liquid mixture contains 20% benzene,
what is the final temperature?
Txy diagram

P = 1 atm

35
Example: Calculations using Txy Diagrams - 2
Using the Txy diagram, estimate the dew-point temperature and equilibrium liquid
composition associated with a vapor mixture of benzene and toluene containing 40
mole% benzene at 1 atm. Next, if condensation proceeds until the remaining vapor
contains 60% benzene, what is the final temperature?
Txy diagram

P = 1 atm

36