Chemical Calculations 1

Lecture
Single Phase Systems
The following methods can be used to determine a
physical property of a process material:

• Look it Up – when you need a value for a

physical property of a substance-whether it be a
density, vapor pressure, solubility, or heat
capacity-there is a good chance that someone,
somewhere has measured this property and
published the result.
• Estimate It
• Measure It
Ideal Gases
• An equation of state relates the molar
quantity and volume of a gas to temperature and
pressure.
• The simplest and most widely used of these
relationships is the ideal gas equation of
state (the familiar PV=nRT)
The Ideal Gas Equation of State
• The ideal gas equation of state can be derived
from the kinetic theory of gases by assuming
that gas molecules have a negligible volume,
exert no forces on one another, and collide
elastically with the walls of their containers.
• The ideal gas equation of state is an
approximation
The Ideal Gas Law
• Under conditions such that the average distance
between the molecules in a substance is great
enough to neglect the effect of the
intermolecular forces and the volume of the
molecules themselves, a gas can be termed as
ideal gas.
The Ideal Gas Law
• Boyle’s Law: (at const. T & n)

• Charles Law: (at const. P & n)

• Avogadro’s Law: ( at const. T & P)

Gas Law Relationships

Alternative Form
Dalton’s Law of Partial Pressure
Mole Fraction
Standard Temperature and
Pressure
• For an ideal gas at an arbitrary temperature T
and pressure P, PV=nRT (equation 1);
• For the same ideal gas at a specified reference
temperature Ts (0◦C=273K) and pressure Ps(1
atm) (referred to as standard temperature and
pressure or STP), PsṼs=RTs (equation 2);
• The first equation divided by the second yields
𝑃𝑉 𝑇
= 𝑛
𝑃𝑠Ṽ𝑠 𝑇𝑠
Ideal Gas Mixtures
• The partial pressure of a component in an ideal
gas mixture is the mole fraction of that
component times the total pressure;
• The partial pressure of the components of an
ideal gas mixture add up to the total pressure
(Dalton’s Law)
• The volume fraction of a substance in an ideal
gas mixture equals the mole fraction of this
substance (Amagat’s Law)
Problem 5.25/p 219
• An ideal gas mixture contains 35% helium, 20%
methane, and 45% nitrogen by volume at 2.00
atm absolute and 90◦C. Calculate:
a. The partial pressure of each component;
b. The mass fraction of methane;
c. The average molecular weight of the gas;
d. The density of the gas in kg/m3.
Equations of State for Non Ideal
Gases
• The ideal gas is the basis of the simplest and
most convenient equation of state;
• Solving it is trivial, regardless of which variable
is unknown, and the calculation is independent
of the species of gas and is the same for single
and mixtures.
Real Gas Relationships
• In this section, we introduce several more
complex but more accurate equations of state
for single species:
1. Virial equations
2. The van der Waals equation
3. The Soave-Redlich-Kwong equation
4. Use of Compressibility factors
5. Kay’s Rule-a method for performing PVT
calculations on gas mixtures
Introduction
• The ideal gas is the basis of the simplest and
most convenient equation of state.
• Its shortcoming is that it can be seriously
inaccurate.
• At a sufficiently low temperature and/or a
sufficiently high pressure, a value of V
predicted with the ideal gas equation could be
off by a factor or two or three or more in either
direction.
Critical Temperature and Pressure
• In general, the highest temperature at which a
species can con-exist in two phases (liquid and
vapor) is the critical temperature of that species,
Tc, and the corresponding pressure is the critical
pressure Pc.
• A substance at Tc and Pc is said to be at its
critical state.
Critical state (point) mean?
• The critical state for the gas-liquid transition is
the set of physical conditions at which the
density and other properties of the liquid and
vapor becomes identical. (Himmelbleau)
Vapor or Gas????
• A vapor is a gaseous species below its critical
temperature
• A gas is a species above its critical temperature
at a pressure low enough for the species to be
more like a vapor than a liquid.
• Substances at temperatures above Tc and
pressures above Pc are referred to as
supercritical fluids.
Supercritical Fluids ????
• A supercritical fluid, that is, a compound in a
state above the critical point, combines some of
the properties of both gases and liquids.
(Himmelbleau)
Virial Equations of State
• A virial equation of state expresses the
quantity PṼ/RT as a power series in the inverse
of specific volume (Felder)
• ….classical equations of state are formulated as a
power series (the virial form) with p being a
function of 1/V with 3 to 6 coefficients
(Himmelbleau)
Virial Equations of State
Virial Equations of State
• Other forms of the virial equation of state have
been developed for specific compounds and
mixtures (Example: the Benedict-Webb-Rubin
(BWR) equation
Cubic Equation of State
• A number of analytical PVT relationships are
referred to as cubic equation of state
because when expanded, they yield third order
equations for the specific volume.
• Examples are van der Waals, Redlich-
Kwong, Soave-Redlich-Kwong (SRK) and
Peng-Robinson equations
Van der Waals Equation of State
SRK Equation of State
Problem No: 5.59/P 231 (Felder)
• The absolute pressure within a 35.0 liter gas
cylinder should not be exceed 51.0 atm. Suppose
the cylinder contains 50.0 mol of a gas. Use SRK
equation of state to calculate the maximum
permissible cylinder temperature if the gas is (a)
CO2 & (b) Ar. Finally calculate the values that
would be predicted by the ideal gas equation of
state.
The Compressibility Factor Equation of
State
• The compressibility factor of a gaseous species is
defined as the ratio (z=PV/RT)
• If the gas behaves ideally, z=1. The extent to
which z differs from 1 is a measure of the extent
to which the gas is behaving non ideally.
• A factor that compensates for the non ideality of
the gas, can be looked at as a measure of non
ideality.
The Law of Corresponding States and
Compressibility Charts
1. Look up the critical temperatures, Tc, and
critical pressure, Pc, of the species.
2. Calculate the reduced temperature (Tr=T/Tc)
and reduced pressure (Pr=P/Pc).
3. Look up the value of z on a generalized
compressibility chart, which plots z versus Pr
for a specified Tr.
Reduced Variables
• Other terms with which you should become
familiar are the reduced variables.
• These corrected, or normalized, conditions
of temperature, pressure, or volume, normalized
(divided) by their respective critical conditions,
as follows:
Reduced Values
Problem No. 5.65/P 233 (Felder)
• A certain gas has a molecular weight of 30.0, a
critical temperature of 310 K, and a critical
pressure of 4.5 MPa. Calculate the density in
kg/m3 of this gas at 465 K and 9.0 MPa (a) if the
gas is ideal and (b) if gas obeys the law of
corresponding states
Non Ideal Gas Mixtures
• Kay’s Rule estimates pseudo critical properties
of mixtures as simple average of pure
component critical constants. (Felder)
• In Kay’s Method, pseudo critical values for
mixtures of gases are calculated on the
assumption that each component in the mixture
contributes to the pseudo critical value in the
same proportion as the number of moles that
component (Himmelbleau)
Problem No. 5.79/P235 (Felder)
• A process stream flowing at 35 kmols/hr
contains 15 mole% hydrogen and the remainder
1-butene. The stream pressure is 10.0 atm
absolute, the temperature is 50ºC, and the
velocity (µ) is 150 m/min. Determine the
diameter (in cm) of the pipe transporting this
stream, using Kay’s rule in your calculations.
Ch.E. Calculation 1 Lec Assignment
• Answer the following Problems in Chapter 5
from Felder;
• 5.6, 5.16, 5.26, 5.30,5.58, 5.66, 5.74, 5.80
• Submission will be on October 7, 2017;
• Use your sketch pad for answers.