Chapter 6-Single Phase Systems 1

SKF 1113 - Material Balances
Single Phase Systems

Kamarul ‘Asri Ibrahim, PhD
Single Phase System

© copyright PCS-FKKKSA Page 1
Topic Outcome
  On successful completion of this unit, the students should be able to:
  Determine the mole of gas from the partial pressure (Dalton’s Law) and
partial volume (Amagat’s Law).
  Discuss the ideal gas law PV=RT and apply it to calculations involving
ideal gas and ideal gas mixtures.
  Describe real gases and the compressibility factor and apply them for
solving mass balance problems.
  Explain virial equation of state and use the equations in solving mass
balance problems.
  Determine the number of mole in gas and vapor streams using PVT
relationship.
Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

PCS -
How to get data?

  Look it up
  Perry’s Chemical Engineering Handbook, 6th Edition, R.H. Perry and D.W. Green
Eds, McGraw-Hill, New York, 1984
  Handbook of Chemistry and Physics, 66th Edition, R.C. Weast, Ed., Chemical
Rubber Company, Boca Raton, Fl, 1985
  The properties of Gases and Liquids, 3rd Edition, R.C. Reid, J.M. Praustniz, and
T.K. Sherwood, McGraw Hill, New York, 1977
  Estimate it
  In the book of properties of gases summarize a large number of empirical
correlations that express physical properties of a mixture in the term pure
component properties and the mixture composition.
  Measure it
  When no information from literature or precision greater than that provided
by general estimation, the only recourse is to determine the property
experimentally.
Single Phase System

Liquid and Solid Densities
  Liquid and Solids  Incompressible

  Changes in T or P does not cause significant changes in liquid and solid
densities
  See appendix B.1 for solid and liquid densities
  Additive :
  Properties of a mixture can be assumed as the following formula
(assumption)
n
1 x
=∑ i
ρ i =1 ρi
Single Phase System


PCS -
Ideal Gases
  Density and Specific Volume of liquid and solid do not change with
pressure and temperature
  For Gas and Vapor we need to know the PVT relationship
  Pressure
  Temperature
  Specific Volume
  Problem require PVT relationship

  Propane at 120oC and 2.3 bars passes through flow meter that reads 250 L/min.
What is the mass flow rate of the gas?
  A pure hydrocarbon gas fills a 2-liter vessel at 30oC with an absolute pressure of
25 atm. How many moles of gas are contained in the vessel?
  Calculate the volume in liters occupied by 100g of N2 at 23oC and 3 psig using
ideal gas behavior
Single Phase System

Ideal Gas Law

  Equation of state relates the quantity (mass or moles) and
volume of gas with temperature and pressure
  The simplest and mostly used is ideal gas law
PV = nRT
P = absolute pressure of the gas

V = volume or volumetric flow rate of gas
n = number of moles or molar flow rate of the gas
R = the gas constant
T = absolute temperature of gas
  Only applicable at low pressure and high temperature
Single Phase System

PCS -
Ideal Gas Law

  The equation can also be written as
where = V/n is the molar volume of the gas
  Any gas is presented by the above equation is known as an

ideal gas or perfect gas
  1 mol of ideal gas at 0oC and 1 atm occupies 22.415 L,

whether the gas is argon, nitrogen, or any other single
species or mixture of gases
Single Phase System

Application of Ideal Gas Law

Calculate the volume occupied by 88 lb of CO2 at a pressure of
32.2 ft of water and at 15oC
88 lb CO 2 1 lb mol CO 2 44.59 ft H 2 O ft 3 288 K

V=
44 lb CO 2 (lb mol)(K) 32.2 ft H 2 O
V = 798 ft 3 CO 2
Single Phase System


PCS -
Gas Reaction Sample Problem (1)

Ammonia (NH3) gas can be synthesized from N2(g) and H2(g).
What volume of ammonia at 450 kPa and 80°C can be obtained
from the complete reaction of 7.5 kg hydrogen?
First we need a balanced equation:

N2(g) + 3H2(g) → 2NH3(g) Basis: 7500 g H2
7500 g H 2 1 mol H 2 2 mol NH 3

nNH = = 2475 mol NH 3
3
2.02 g H 2 3 mol H 2
L.KPa
(2475 mol)(8.31 )(353 K)
nRT mol.K
VNH = = = 16135 L NH 3
3
P (450 KPa)
Single Phase System
Standard Conditions
  Using PVT equation is easy provided you have a set of R constant
value with different units.
  A way to avoid this is by dividing the gas law from process condition
with given chosen reference condition
Standard Conditions for gases
System Ts Ps Vs ns
SI 273 K 1 atm 0.022415 m3 1 mol
CGS 273 K 1 atm 22.415 L 1 mol
American 492oR 1 atm 359.05 ft3 1 lb-mole
Single Phase System


PCS -
Standard Temperature and Pressure (STP)

  Reference temperature (0oC, 273K, 32oF and 492oR) and
pressure (1 atm) are commonly known as STP
  The other related values is easy to commit to memory
like the relation of
Vs m3 (STP) liters(STP) ft 3 (STP)

= 0.0224 ⇔ 22.415 ⇔ 359
ns mol mol lb − mole
Example
Butane (C4H10) at 360oC and 3 atm (absolute) flows into a reactor at
a rate of 1100 kg/h. Calculate the volumetric flow rate (m3/h) of
this stream using conversion from standard conditions.
Single Phase System

Ideal Gas Mixtures – Dalton’s Law

  Suppose nA moles of substance A, nB moles of B and nC moles of C
and so on, are contained in a volume V at temperature T and total
pressure P.
  The partial pressure pA of A in the mixture are defined as
pA : The pressure exerted by nA moles of A alone in the same total

volume V at the same temperature T
From ideal gas law : PV = nRT

From partial pressure: pAV = nART
pA nA
Dividing the second equation with first : = = yA or pA = yA P
P n
Thus the ideal partial pressure of ideal gas add up to the total pressure P
pA + pB + pC + … = ( yA + yB + yC + …) P = P
Single Phase System

PCS -
Ideal Gas Mixture – Amagat’s Law

  Suppose nA moles of substance A, nB moles of B and nC moles of C
and so on, are contained in a volume V at temperature T and total
pressure P.
  The partial volume vA of A in the mixture are defined as
vA : The volume that would be occupied by nA moles of A alone at the

total pressure P at the same temperature T of the mixture
From ideal gas law : PV = nRT

From partial pressure: PvA = nA RT
vA n A
Dividing the second equation with first : = = yA or vA = yAV
V n
Thus the ideal partial volume of ideal gas add up to the total volume V
vA + vB + vC + … = ( yA + yB + yC + …)V = V
Single Phase System
Working Session 1
CH4 burns in O2, producing CO2 and H2O(g). A 1.22 L CH4
cylinder, at 15°C, registers a pressure of 328 kPa.
a.  What volume of O2 at STP will be required to react
completely with all of the CH4?
b.  How many grams of H2O(g) are produced?
c.  What volume of CO2 (at STP) is produced if only 2.15 g
of the CH4 was burned?
Single Phase System


PCS -
Working Session 2
1.  What volume of oxygen at STP is needed to completely
burn 15 g of methanol (CH3OH) in a fondue burner?
(CO2 + H2O are products)
2.  When sodium chloride is heated to 800°C it can be
electrolytically decomposed into Na metal & chlorine (Cl2)
gas. What volume of chlorine gas is produced (at 800°C
and 100 kPa) if 105 g of Na is also produced?
3.  What mass of propane (C3H8) can be burned using 100 L
of air at STP? Note: 1) air is 20% O2, so 100 L of air
holds 20 L O2, 2) CO2 and H2O are the products of this
reaction.
Single Phase System

Working Session 3
4.  A 5.0 L tank holds 13 atm of propane (C3H8) at 10°C.
What volume of O2 at 10°C & 103 kPa will be required to
react with all of the propane?
5.  Nitroglycerin explodes according to:
4 C3H5(NO3)3(l) 12 CO2(g) + 6 N2(g) + 10 H2O(g) + O2(g)
a) Calculate the volume, at STP, of each product formed
by the reaction of 100 g of C3H5(NO3)3.
b) 200 g of C3H5(NO3)3 is ignited (and completely
decomposes) in an otherwise empty 50 L gas
cylinder. What will the pressure in the cylinder be if
the temperature stabilizes at 220°C?
Single Phase System


PCS -
Material Balance on an Evaporator-Compressor
Liquid acetone (C3H6O) is fed at a rate of 400 liters/min into a heated

chamber, where it evaporates into a nitrogen stream. The gas leaving the
heater is diluted by another nitrogen stream flowing at a measured rate of
419 m3 (STP)/min. The combined gases are then compressed to a total
pressure Pgauge = 6.3 atm at a temperature of 325oC. The partial pressure of
acetone in this stream is pa = 501 mmHg. Atmospheric pressure is 763 mm Hg
  What is the molar composition of the stream leaving the compressor?

  What is the volumetric flow rate of nitrogen entering the evaporator if T
= 27oC and Pgauge = 475 mm Hg
Density of liquid acetone=791 g/L
Single Phase System

Solution of Evaporator -Compressor
V1 (m3/min)
q1 (mol N2/min) q4 (mol/min)
27oC, 475 mmHg Compressor ya (mol C3H6O/mol)
Evaporator 1 - ya (mol N2/mol)
400 L/min C3H6O 6.3 atm gauge, 325oC
q2 (mol /min) pa = 501 mm Hg
419 m3(STP) N2/min

q3 (mol/min)
Single Phase System


PCS -
Real Gas
  As the temperature of a gas decreases and pressure increases, the ideal
gas law provides an increasing poor description
  To avoid this error - is by using real gas correction factor such as
(1) Virial Equation of State (Benedict-Webb-Rubin, BWR)
(2) Cubic Equation of State (Soave-Redlich-Kwong, SRK)
(3) Compressibility Factor of equation of State (PV = znRT)
(4) For real gas mixtures use Kay’s Rule
Single Phase System

Critical Temperature Tc and Pressure Pc
  The highest temperature at which species can coexist 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.
  Substance at temperature above and pressure above are

referred to as Supercritical Fluids.
  Vapor is a gaseous species below its Critical Temperature.
  Gas is a species above its Critical temperature
Single Phase System


PCS -
Properties for some chemicals
Single Phase System

Properties for some chemicals
Single Phase System


PCS -
Virial Equation of State (BWR)

  A Virial equation of state is an equation of the form
  The coefficient B(T) is called the second virial equation, C(T) is the third
virial equation, and so on
  If B = C= D = 0, then we have ideal gas law
  Benedict-Webb-Rubin (BWR) equation, which contain 8 constants
  Values of Ao, Bo, Co, a, b, c, α, γ is tabulated in the book pp 195 and in

Reid, Prausnitz and Sherwood book (Properties of Gases)
Single Phase System
Cubic Equation of State (SRK)

  One of the most used of this equation is the Soave modification of
Redlich-Kwong equation
  Values of a, b is evaluated by using critical temperature and critical

pressure which given in Table B.1 in Appendix B
( )
2
α = ⎡⎣1 + m 1 − T / Tc ⎤⎦ where m = 0.48508 + 1.55171ω - 0.15613ω 2
  Value of accentric factor (ω) is given in Textbook

Single Phase System

PCS -
Pitzer Acentric Factors

Compound Acentric Factor, ω
Ammonia 0.250
Argon -0.004
Carbon Dioxide 0.225
Carbon Monoxide 0.049
Chlorine 0.073
Ethane 0.098
Hydrogen Sulfide 0.100
Methane 0.008
Methanol 0.559
Nitrogen 0.040
Oxygen 0.021
Propane 0.152
Sulfur Dioxide 0.251
Water 0.344
Single Phase System
Compressibility Factor Equation of State

  An equation of state that retains the simplicity of the ideal gas law but
describe the PVT behavior of real gas
PV = znRT or PV̂ = zRT
  The coefficient z is called the compressibility factor, and the equation is

known as the compressibility factor equation of state
  A value of z = 1 correspond to ideal gas behavior
  The compressibility factor of a gas depends on the gas temperature
and pressure
  For real gases, z < 1 at low pressure and z > 1 at high pressure
  Values of z(T,P) for air, argon, CO2, CO, H2, CH4, N2, O2 are given in
Perry’s Chemical Engineers’ Handbook, pp 3-112 to 3-118
Single Phase System


PCS -
Estimation of Compressibility Factors

(1) Look up or estimate the critical temperature (Tc) and critical pressure (Pc)
(2) If the gas is hydrogen or helium, determine the pseudo critical constant
from the empirical formulas
  (Tc)adjusted = Tc + 8 K
  (Pc) adjusted = Pc + 8 atm
  The above equation are known as Newton’s correction
(3) Calculate reduced values of the two known variables (T and P, T
and , or P and ) using the formulas and use compressibility charts
  Reduced Temperature: Tr = T/Tc
  Reduced Pressure: Pr = P/Pc
  Ideal Reduced Volume:
  All temperature and pressure used for this formula must be absolute
Single Phase System

Compressibility Factor
Single Phase System


PCS -
Compressibility Factor (Low Z)
Single Phase System

Compressibility Factor Medium Z)
Single Phase System


PCS -
Compressibility Factor (High Z)
Single Phase System

Real Gas Mixtures: Kay’s Rule

  Technique to be used when we have mixture of real gas
PV = zmnRT or PV̂ = z m RT
  Calculate the pseudo critical constant of gas mixture component

  Pseudo critical Temperature: Tc’ = yaTca + ybTcb + ycTcc +...
  Pseudo critical Pressure: Pc’ = yaPca + ybPcb + ycPcc +...
  If the temperature and pressure of the mixture are known, calculate
  Pseudoreduced Temperature: Tr‘ = T/Tc’
  Pseudoreduced Pressure: Pr‘= P/Pc’
  Use the generalized compressibility chart to obtain zm
  All pseudo critical constant of mixture are simply empirical parameters

and do not have any physical significance
Single Phase System

PCS -

Chapter 6-Single Phase Systems 1

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SKF 1113 - Material Balances

Single Phase Systems

Single Phase System

Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

How to get data?

Single Phase System

Liquid and Solid Densities

 Liquid and Solids  Incompressible

Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

 Problem require PVT relationship

Single Phase System

Ideal Gas Law

P = absolute pressure of the gas

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

Ideal Gas Law

where = V/n is the molar volume of the gas

 Any gas is presented by the above equation is known as an

 1 mol of ideal gas at 0oC and 1 atm occupies 22.415 L,

Single Phase System

Application of Ideal Gas Law

88 lb CO 2 1 lb mol CO 2 44.59 ft H 2 O ft 3 288 K

Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

Gas Reaction Sample Problem (1)

First we need a balanced equation:

7500 g H 2 1 mol H 2 2 mol NH 3

Standard Conditions for gases

Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

Standard Temperature and Pressure (STP)

Vs m3 (STP) liters(STP) ft 3 (STP)

Single Phase System

Ideal Gas Mixtures – Dalton’s Law

pA : The pressure exerted by nA moles of A alone in the same total

From ideal gas law : PV = nRT

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

Ideal Gas Mixture – Amagat’s Law

vA : The volume that would be occupied by nA moles of A alone at the

From ideal gas law : PV = nRT

Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

Single Phase System

Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

Material Balance on an Evaporator-Compressor

Liquid acetone (C3H6O) is fed at a rate of 400 liters/min into a heated

 What is the molar composition of the stream leaving the compressor?

Density of liquid acetone=791 g/L

Single Phase System

Solution of Evaporator -Compressor

419 m3(STP) N2/min

Single Phase System

Instructor: Prof Dr. Kamarul ‘Asri Ibrahim

(1) Virial Equation of State (Benedict-Webb-Rubin, BWR)

(2) Cubic Equation of State (Soave-Redlich-Kwong, SRK)

(3) Compressibility Factor of equation of State (PV = znRT)

(4) For real gas mixtures use Kay’s Rule

Single Phase System

Critical Temperature Tc and Pressure Pc

 The highest temperature at which species can coexist in

 A substance at Tc and Pc is said to be at its critical state.

 Substance at temperature above and pressure above are

  Liquid and Solids  Incompressible

  Problem require PVT relationship

  Any gas is presented by the above equation is known as an

  1 mol of ideal gas at 0oC and 1 atm occupies 22.415 L,

  What is the molar composition of the stream leaving the compressor?

  The highest temperature at which species can coexist in

  A substance at Tc and Pc is said to be at its critical state.

  Substance at temperature above and pressure above are

  Values of Ao, Bo, Co, a, b, c, α, γ is tabulated in the book pp 195 and in

  Values of a, b is evaluated by using critical temperature and critical

  Value of accentric factor (ω) is given in Textbook

  The coefficient z is called the compressibility factor, and the equation is

  Ideal Reduced Volume:

  Calculate the pseudo critical constant of gas mixture component

  All pseudo critical constant of mixture are simply empirical parameters