K Value and De Priester chart

The Volume of Liquid Expanded (VLE) and the K-value (distribution coefficient or equilibrium
ratio) are concepts related to phase equilibrium in thermodynamics, particularly in the separation
processes like distillation. The VLE is a condition where liquid and vapor phases coexist in
equilibrium. The K-value (or equilibrium constant) is used to describe how a component
distributes itself between the vapor and liquid phases at equilibrium.
The K-value is given by the ratio:
𝐲𝒊
Ki =
𝐱𝒊
Where:
Ki is the K-value of component i,
Yi is the mole fraction of component i in the vapor phase,
Xi is the mole fraction of component i in the liquid phase.

K-Value Correlations
K-values depend on temperature, pressure, and the nature of the components. Various empirical
and theoretical correlations exist to estimate K-values for components in multi-component
systems. Some common methods include:
1. Raoult's Law (for Ideal Systems):
∗
Ki =
Where Pi∗/P is the vapor pressure of component i and P is the total system pressure.
Raoult's law assumes ideal behavior, which works well for systems that are nearly ideal.
2. Wilson, NRTL, or UNIQUAC Models (for Non-Ideal Systems): These models take into
account the non-ideal behavior of components in a mixture by using activity coefficients.
3. DePriester Charts: These charts provide graphical methods for estimating K-values based
on experimental data for hydrocarbons, typically used in gas processing.
4. Thermodynamic Models (EOS-based): Equations of state (EOS) like the Peng-Robinson
EOS or Soave-Redlich-Kwong (SRK) EOS can be used to calculate K-values. These
methods are widely used for non-ideal systems and for high pressures.
Ki=exp (VLΔP|RT)
Where VL is the molar volume of the liquid phase, ΔP is the pressure difference, R is the
gas constant, and T is the temperature.

Applications
 Distillation design: In distillation columns, K-values help predict the composition of
vapor and liquid streams at each stage of the column.
  Flash calculations: K-values are critical in flash vaporization processes, where a liquid
mixture is partially vaporized to separate components.
 Thermodynamic modeling: K-values are used in phase equilibrium calculations to model
separation processes in chemical engineering.

Flash Calculations
Flash calculations are used to determine how a multi-component mixture behaves when it is
partially vaporized or condensed. These calculations are common in chemical process design and
operation, especially in distillation, absorption, and gas processing.
In a flash calculation, a feed stream of known composition, pressure, and temperature is fed into
a vessel (flash drum). The mixture is allowed to equilibrate, and a portion of the liquid vaporizes
(or the vapor condenses), resulting in two phases: vapor and liquid. The goal of the calculation is
to determine the amounts and compositions of both phases in equilibrium.

Key Assumptions
 The vapor and liquid phases are in thermodynamic equilibrium, meaning that for each
component in the mixture, the chemical potential (or fugacity) of the vapor equals that of
the liquid.
 The system operates at constant temperature and pressure (isothermal and isobaric
conditions).

Flash Calculation Basics

The primary steps in flash calculation involve determining:
1. Vapor-Liquid Equilibrium (VLE): At equilibrium, the relationship between the vapor
and liquid mole fractions for each component is described by the K-value (equilibrium
ratio).
𝐲𝒊
Ki =
𝐱𝒊
Where:
Ki is the equilibrium ratio (K-value) of component iii,
yi is the mole fraction of component iii in the vapor phase,
xi is the mole fraction of component iii in the liquid phase.
2. Material Balance: The total mass or mole balance across the flash drum can be written
as:
F=V+L
Where:
o F is the feed flow rate,
o V is the vapor flow rate,
o L is the liquid flow rate.
 3. Component Material Balance: For each component iii in the mixture:
Fzi = Vyi+Lxi
Where:
o zi is the mole fraction of component iii in the feed,
o yi and xi are the mole fractions of component iii in the vapor and liquid phases,
respectively.
4. Equilibrium Relationship: The equilibrium relationship links the liquid and vapor
compositions through the K-values:

Applications
Flash calculations are essential in many areas of chemical engineering, including:
 Distillation: Used to model the initial separation of a mixture into vapor and liquid phases.
 Gas-liquid separation: For processes like gas sweetening and dehydration.
 Crude oil stabilization: In petroleum refining, flash calculations help separate crude oil
into lighter and heavier fractions.
 Refrigeration and liquefied gas plants: Flash calculations determine phase splits in
various parts of the process.

The DePriester chart is a graphical tool used to estimate K-values (equilibrium ratios) for
hydrocarbon systems at equilibrium. It is particularly useful for engineers working with vapor-
liquid equilibria in distillation, flash calculations, and other separation processes involving
hydrocarbons.
The DePriester chart was developed based on experimental data for hydrocarbons, and it helps in
estimating the K-values of individual components at specific temperatures and pressures. These
charts are widely used in the oil and gas industry, as well as in chemical engineering processes.

What is a K-Value?
The K-value or equilibrium ratio is defined as the ratio of the mole fraction of a component in
the vapor phase to the mole fraction in the liquid phase at equilibrium:
Ki=yixi
Where:
 Ki is the equilibrium ratio of component iii,
 yi is the mole fraction of component iii in the vapor phase,
 xi is the mole fraction of component iii in the liquid phase.
K-values vary with pressure, temperature, and the nature of the mixture, which is where the
DePriester chart comes in handy.
Structure of the DePriester Chart
A DePriester chart is typically a log-log plot where:
 The x-axis represents the pressure in units like psia (pounds per square inch absolute).
 The y-axis represents the K-value for a particular hydrocarbon component.
 A series of curves on the chart represent different temperatures.
Each curve corresponds to a constant temperature, and different hydrocarbons will have their own
set of curves (often grouped together for convenience).

Using a DePriester Chart

1. Identify the Component: DePriester charts are usually plotted for common hydrocarbons
(e.g., methane, ethane, propane, butane, etc.). You need to know which component you're
working with to use the appropriate set of curves on the chart.
2. Locate the Operating Pressure: Find the pressure of the system on the x-axis (in psia or
bar). This will be the pressure at which the mixture is in equilibrium.
3. Identify the Temperature: Identify the constant temperature curve that corresponds to
your system’s temperature on the chart. The temperature is usually in degrees Fahrenheit
or Celsius.
4. Read the K-Value: Once the pressure and temperature are located, trace the lines from
both points until they intersect. The intersection point will give you the K-value
(equilibrium ratio) for the component at those specific conditions.

Example of Using a DePriester Chart

Suppose you are working with a system containing propane at a pressure of 300 psia and a
temperature of 120°F, and you need to estimate the K-value for propane.
1. Look at the DePriester chart for propane.
2. On the x-axis, locate 300 psia.
3. On the y-axis, find the curve that corresponds to 120°F.
4. Where these two intersect, read off the K-value for propane at these conditions (for
example, it could be 0.6).

Applications of the DePriester Chart

1. Flash Calculations: In flash separators or vapor-liquid separators, DePriester charts help
estimate the K-values of hydrocarbons, which are crucial for calculating phase equilibrium.
2. Distillation Design: DePriester charts provide a quick and reliable method to determine
K-values during the design of distillation columns, especially for hydrocarbon mixtures.
The K-values help in determining how much of each component will stay in the liquid or
vapor phase at each stage of the column.
 3. Gas-Liquid Separation: In natural gas processing, DePriester charts are used to estimate
how much of a gas will condense at a given pressure and temperature, which is important
in dehydration and gas sweetening processes.
4. Crude Oil Stabilization: The charts can be applied in crude oil stabilization processes to
estimate phase splits during the flash of lighter hydrocarbons from heavier fractions at
various pressures and temperatures.

Limitations
1. Applicability: The DePriester chart is primarily applicable for hydrocarbon systems. It
is not suitable for non-hydrocarbons or polar compounds like water, ammonia, or alcohols.
2. Approximation: The K-values obtained from DePriester charts are approximations. For
more precise calculations, especially for non-ideal systems, more advanced
thermodynamic models (e.g., equations of state) are often required.
3. Pressure and Temperature Limits: DePriester charts are valid only within the specific
pressure and temperature ranges for which the experimental data were collected. Outside
these ranges, the charts are less reliable.

Conclusion
DePriester charts provide a quick, graphical method to estimate K-values for hydrocarbons at
various pressures and temperatures. They are highly practical for performing phase equilibrium
calculations, particularly in processes involving hydrocarbon separations, like distillation and gas
processing. However, for complex systems or extreme conditions, other methods, such as
thermodynamic models or software simulations, may be required.