Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
Department Chemical Engineering
Year E1
Semester II
Course Name Chemical Process Calculations
Course Code CH1201
Course Credit 3
Name of the Faculty CHINTHAYYANAIDU RUDRAM
Module - 4
Ideal Gas Behaviour
Objectives
To comprehend important principles such as Ideal gas law and Raoult’s law.
Learn to generate vapour – liquid Equilibrium.
Equilibrium
Ideal Gas Law: The pressure, P
P, Molar volume V, and temperature, Tof
of an ideal gas are
related by a simple formula called the ideal gas law.. The simplicity of this relationship is a
big reason why we typically treat gases as ideal, unless there is a good reason to do
otherwise.
Pv = RT -----------(1)
PV = nRT----------
----------(2)
R = PV/nT, ---------
---------(3)
where P= Pressure of the gas,
T = absolute temperature (K or 0R)
n = no of moles,
v= Molar volume(volume per mole),
V – volume of n moles,
R – Universal Gas constant
Applications of Ideal Gas Law
When substances exist in the gaseous state two general types of problems arise in
determining the relationships between weight, pressure, temperature, and volume. The first
type is that in which are involved only the last three variables — pressure, temper
temperature, and
volume. For example, a specified volume of gas is initially at a specified temperature and
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
pressure. The conditions are changed, two of the variables in the final state being specified,
and it is desired to calculate the third. For such calculat
calculations
ions it is not required to know the
weight of the gas. The second, more general type of problem involves the weight of the
gas.
A specified weight of substance exists in the gaseous state under conditions, two of which
are specified and the third is to be calculated. Or, conversely, it is desired to calculate the
weight of a given quantity of gas existing at specified conditions of temperature, pressure,
and volume. Problems of the first type, in which weights are not involved, may be readily
solved by meanss of the proportionality indicated by the gas law. Equation (2) may be
applied to n moles of gas at conditions, P1, V1, T1and also at conditions P2, V2, T2.
P1V1= n1 RT1
P2V2= n2 RT2
(P1V1)/(n1T1) = (P2 V2)/(n2 T2)
Standard Conditions: An arbitrarily specified standard state of temperature and pressure
serves two purposes. It establishes the normal molal volume constant required in the
system of calculation described in the preceding section. It also furnishes convenient
specifications under
nder which quantities of gases may be compared when expressed in terms
of volumes. Some such specification is necessary because of the fact that the volume of a
gas depends not only on the quantity but on the temperature and pressure as well.
Volume of gases
es at standard conditions are given below
Volume of 1 g mol at standard conditions is 22.414. litres
Volume of 1 lbmol at standard conditions is 359 ft3
Volume of 1 K mol at standard conditions is 22.414. m3
Standard conditions
Temperature Pressure
o
0C 1 atm
273.16 K 760 mm of Hg
32 oF 29.92 in Hg
o
491.69 R 14.70 psi
Gaseous Mixtures
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
Partial Pressure(pA) of a component gas that is present in a mixture of gases is the
pressure that would be excreted by that component gas if it alone were present in the same
volume and at the same temperature as the gas mixture.
Pure Component Volume (Va) of the component gas that is present in a mixture of gasses
is the volume that would be occupied by that component gas if it alone were present at the
same pressure
re and the temperature as the mixture.
Dalton’s Law: Total pressure excreted by a gaseous mixture is equal to the some of the
partial pressure
P = pA + pB + pC…..
Amagot Or Ledue’s Law:: Total volume occupied by a gaseous mixture is equal to the
some of the pure volumes
V= VA + VB + VC…..
Where small moral volumes are encountered, such that the ideal gaslaw does not apply
either Dalton's or Amagat's law may apply, but both laws apply ssimultaneously
imultaneously only for
ideal gases. Under such conditions pressures may not be additive, because the introduction
of additional molecules into a gas
gas-filled
filled container may appreciably affect the pressure
exerted by those already there. The presence of new mo
molecules
lecules will reduce the space
available for the free motion of those originally present and will exert attractive forces on
them. Similarly, if quantities of two gases at the same pressure are allowed to mix at that
same pressure, the like molecules of eac
each
h gas will be separated by greater distances and
willl be in the presence of unlike molecules, which condition may alter the order of
attractive forces existing among them. As a result, the volume of the mixture may be quite
different from the sum of the original
original volumes. These same effects are present but
negligible under conditions of large molal volumes and wide separation of molecules.
Where conditions are such that the ideal gas law is applicable:
pA = nART/V
nA = no. of moles of component A in mixture
Similar equations represent the partial pressures of components B, C,etc.
etc. Combining th
these
equations with Dalton's law
P = (nA + nB + nC + ---------)) RT/V
pA/P = nA/(nA + nB +nC)
pA = XA P
XA = nA/(nA + nB +nC)
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
XA = mole fraction of Component A
Similarly,
Where conditions are such that the ideal gas law is applicable
P VA = nA RT
P VB = nB RT and So on
P(VA + VB+……) = (nA + nB +……) RT
VA/V = (nA)/ (nA + nB +……)
VA = XA V
Average Molecular Weight of a Gaseous Mixture.
Mixture
A certain group of components of a mixture of gases may in many cases pass through a
process without being changed in composition or weight. For example, in a drying process,
dry air merely serves as a carrier for the vapor being removed and undergoes no change in
composition or in weight. It is frequently convenient to treat such a mixture as though it
were a single gas and assign to it an average molecular weight which may be used for
calculation of its weight and volume relationships. Such an average molecular weight has
no physical significance
ficance from the standpoint of the molecular theory and is of no value if
any component of the mixture takes part in a reaction or is altered in relative quantity. The
average molecular weight is calculated
culated by adopting a unit molar quantity of the mixture as
the basis of calculation.
lation. The weight of this molar quantity is then calculated and will
represent
present the average molecular w
weight.
eight. By this method the average molecular we
weight of
air is found to be 29.0
Vapour Pressure:: If the vapour and liquid of a pure component
component are in equilibrium, there
the equilibrium pressure excreted by the liquid is called vapour pressure.
Antoine Equation
𝐵
log 𝑃𝑠𝑎𝑡 = 𝐴 −
𝑇+𝐶
Equilibrium state given the limit of an operation
Equilibrium conditions represent end points of any naturally occurring process.
Saturated Vapour: A vapour that exists under such conditions that its partial pressure is
equal to its equilibrium pressure is termed as saturated vapour.
Dew Points/ Saturation Temperatu
Temperature:The temperature at which a vapour is saturated is
termed as dew points or saturation temperature.
Super Heat Vapour: The Vapour whose partial pressure is less than its equilibrium
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
vapour pressure is termed as superheat vapour.
Degrees Of Super Heat: The difference between the existing temperature of vapour and
its saturation temperature is known as degrees of super heat.
Wet Vapour: If a saturated vapour is cooled, condensation will result and the vapour plus
entrained liquid is called the wet vapour.
Quality Of Wet Vapour:: Is the fraction that the weight of vapour forms to the total weight
of vapour and entrained liquid associated with it.
X = WV/(WV + WL) and 100x is present quality.
Where x= quality,
WV = Weight of vapour,
WV = Weight of liquid.
Boiling Points:When
When a liquid surface is exposed to a space in which the
the total gas pressure
is less than the equilibrium vapour pressure of the liquid, rapid vaporization known as
boiling takes place.
Normal Boiling Points:The
The temperature at which a liquid boils under a total pressure of 1
atm is termed as normal boiling points.
poin
Clapeyron Equation:
dPsat/dT = λ/(VG-VL)T.
where Psat = Vapour pressure
T = absolute temperature
λ = heat of vaporization at temperature T
VG =Volume of gas
VL = Volume of liquid
Given the relation between Temperature & vapour.
vapour
Heat of Vaporization:is
is the quantity of heat that must be added in order to transform a
substance from the liquid to the vapour state at the same temperature.
Clausius –Clapeyron
Clapeyron Equation
ln (P/P0) = (λ /R) (1/T0 – 1/T), will permit to calculate vapour pressure of a substance
at temperature T if the vapour pressure P0 at another temperature T0 is known together with
the latent heat of vaporization (λ).
).
Reference substance plots Vapour pressure vs temperature plots developed based on
compounds of similar properties.
Duhring lines (Equal pressure reference substance plots): Plotted the tempera
temperature at
which the substance of interest
terest has a given vapour pressure against the temperature at
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
which the reference substance
nce has the same vapour pressure.
COX LINES (Equal Temperature Reference Substance Plots
Plots):Vapour pressure of
reference substance vs. vapour pressure of a substance both at same temperature are plotted
on a Logarithmic scale which results into a straight line Log p of reference substance is
replaced by a specially derived temp scale.
Critical Temperature: The temperature at which a gas can be liquefied or the temperature
above which liquid cannot exists is referred as critical
c temperature.
Critical Pressure: The pressure required to liquefy a gas at its critical temperature is
termed as critical pressure.
Raoult’s Law: States that the equilibrium vapour pressure that is exerted by the
components in a solution is proporti
proportional to the mole fraction of that component.
pi = xipsati
where pi = partial pressure
xi = mole fraction
psati = Vapour pressure.
Vapour – Liquid Equilibrium:
For each component in a binary mixture, one could make a vapour
vapour–liquid
liquid equilibrium
diagram. Such a diagram would graph liquid mole fraction on a horizontal axis and vapour
mole fraction on a vertical axis. In such VLE diagrams, liquid mole fractions for
components 1 and 2 can be represented as x1 and x2 respectively, and vapor mole fract
fractions
of the corresponding components are commonly represented as y1 and y2
Similarly for binary mixtures in these VLE diagrams
We Know as
x 1 + x2 = 1
y1 + y2 = 1
from Daltons law;
Ptot = P1 + P2
Then for each component in the vapor phase:
y1 = P1 / Ptot, y2 = P2 / Ptot
from Raoults law
P1 = x1 P sat1, P2 = x2 P sat2
From above equation x1 = (Ptot- P sat2)/( P sat1-P sat2)
x2= (Ptot- P sat1)/( P sat2-P sat1)
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
y1 = x1 P sat1/Ptot
y1 = [(Ptot- P sat2)/( P sat1-P sat2)] X P sat1/Ptot
y2 = x2 P sat2/Ptot
y2 = [(Ptot- P sat1)/( P sat2-P sat1)] X P sat1/Ptot
Summary
Discussed about the Ideal Gas laws and its applications average molecular weight of a
gaseous mixture. Discuss the Raoults law and VLE data generation.
Solved Problems
01 Calculate the volume occupied by 30lb of chlorine at a pressure 743mm of Hg and
70°F.
Ans Basis: 30lb of Chlorine
Moles=mass/molar mass=30lb/71=0.423lb-mol
mass=30lb/71=0.423lb
Standard Conditions Given Conditions
P1= 760 mm of Hg P2 = 743 mm of Hg
T1 = 32oF+ 460 = 492oR T2 = 70oF+ 460 = 530oR
V1= 359 ft3 V2 = ??
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
n 1 = 1 lbmol n 2 = 0.423
We know as
(P1V1)/(n1T1) = (P2V2)/(n2T2)
V2 = 167 ft3
02 Calculate the weight of 100cu ft of water vapor measured at a pressure of 15.5mm
Hg and 23°C.
(Ans) Basis:100 cu ft of water vapor at 15.5 mm Hg, 23oC
Standard Conditions Given Conditions
P1= 760 mm of Hg P2 = 15.5 mm of Hg
o
T1 = 0 c+ 273 = 273K T2 = 23oC+ 273 = 296K
V1= 359 ft3 V2 = 100 ft3
n 1 = 1 lbmol n 2 = ??
We know as
(P1V1)/(n1T1) = (P2V2)/(n2T2)
n 2 = 0.00523 lb-mole.
Weight of H2O=0.00523×18=0.0942 lb.
3 When heated to 100℃and
and 720 mm of hg pressure 17.2 g of N2O4 gas occupy a
volume of 11,[Link] that the ideal gas law applies, calculate the
％dissociation of N2O4 to NO2.
(Ans) Basis:17.2g of N2O4
weight 17.2 g 0.186mol
Moles of N2O4 = = =
molecularweight 92
Standard Conditions Given Conditions
P1= 760 mm of Hg P2 = 720 mm of Hg
T1 = 0oc+ 273 = 273K T2 = 100oC+ 273 = 296K
V1= 22.4 lit V2 = 11.45 lit
n 1 = 1gmol n 2 = ??
We know as
(P1V1)/(n1T1) = (P2V2)/(n2T2)
n 2 = 0.35lb-mole.
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
gmolofN 2O 4 dissociated
％dissociation = ×100
initialmolesofN 2O 4
0.35 0.18 100
= ×
0.186
=91.3％
4 Calculate the average molecular weight of fuel gas having the following
composition by volume CO2- 13.1％ O2 - 7.7％ N2 - 79.2 %.
(Ans) Basis: 100 mol of fuel gas
Given vol％ data
We know that vol％ =mol％
mol％ of CO2 = 13.1％
13.1
mol fraction of CO2= =0.13
100
mol％ of O2 = 7.7％
7.7
mol fraction of O2 = =0.077
100
mol％ of N2 =79.2％
79.2
mol fraction of N2 = = 0.792
100
Molwt of CO2 =44
Molwt of O2 =32
Molwt of N2 =28
i
[Link] of fuel gas = molfraction [Link] n
i 1
i
=(0.13×44)+(0.077×32)+(0.792×28)
=30.4
5 Calculate the density in pounds/ft3 at 29 in of hg and 30℃ of a mixture of hydrogen and
oxygen which contains 11.1％ H2 by weight
(Ans) Basis: 100 lb of mixture
Given data:
Pressure P = 29 in of hg
Temperature T= 30℃
30
wt％ of H2 = 11.1％
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
Wt of H2 = 11.1 lb
wt 11.1
moles of H2= = =5.55 lbmol
mol .wt 2
Wt of O2=(100-11.1)=88.8lb
11.1)=88.8lb
88.9
moles of O2= = 2.77lbmol
32
Total moles=5.55+2.77 =8.32 lbmol
From ideal gas eqn PV=nRT
Standard Conditions Given Conditions
P1= 29 in of Hg P2 = 29.92 in of Hg
o
T1 = 0 c+ 273 = 273K T2 = 30oC+ 273 = 303K
V1= 359 ft3 V2 = ??
n 1 = 1lbmol n 2 = 100 lbmol
PV 29.92 359 inofhg ft ^3
R= = = 39.34
nT 1 273 lbmol k
at given conditions:
nRT 8.32 39.34 303
Volume v= = =3419.8ft3
p 29
mass 100
Density of mixture= = = 0.0292lbmol/ft3
volume 3419.8
6 Using the vapor equation
𝐵
log 𝑃𝑠𝑎𝑡 = 𝐴 −
𝑇+𝐶
Psat in mm of Hg, T is in oC.
Chemical A B C
Cyclo pentane 15.86 2589.2 231.36
Benzene 15.9037 2789.01 220.79
Prepare the bubble point , dew point and VLE data
Ans Given Antoine eq can be written as
𝐵
log 𝑃𝑠𝑎𝑡 = 𝐴 −
𝑇+𝐶
𝑇= −𝐶
Replace Psat with P
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
𝑇= −𝐶
Substitute P = 760 mm of Hg
Boiling point of cyclopentane : 49.25oC
Boiling point of Benzene: 80.06oC.
Develop the vapor pressure by using Antoine equation in between boiling
point two compounds.
Temperature Vapor Pressure of Vapor pressure of
Cyclopetane Benzene
49.25 760 255.2
60 1077 392
70 1434 551
80 1905 760
By using above data develop VLE data
Temperature x1 = (Ptot- P sat2)/( P sat1-P sat2) y1 = [(Ptot- P sat2)/(
P sat1-P sat2)] X P sat1/Ptot
49.25 1 1
60 0.54 0.76
70 0.235 0.446
80 0 0
7 Calculate the total pressure and composition of the vapour in contact with a solution
at 100oC containing 35 % Benzene and 50 % toluene and 25 % ortho xylene by
wt%.
Vapor pressure data
Benzene: 1340 mm of Hg
Toluene : 560 mm of Hg
Xylene : 210 mm of Hg
Ans Basis: 100 g of mixture
Wt. of Benzene: 35
Wt. of Toluene : 40
Wt. of Xylene : 25
Chemical Lb Lbmol = wt/ molwt P.P = X x V.P Mole fraction
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
(Raoults Law) (P.P/Ptot)
(P.P/
Benzene 35 0.45 536 0.7225
Toluene 40 0.435 218 0.27
Xylene 25 0.236 44 0.005
Total mole 1.120
8 Calculate the composition of liquid mixture which boils liquid mixture 90oC and
760 Torr. Composition of liquid mixture 40 mol % Benzene and 60 % Toulene.
Temp(oC) 60 90
V.P of Benzene 385 1013
V.P of Toulene 140 408
Ans Basis: 100 kmol of mixture
Mole of Benzene: 40 kmol
Mole of Tolulene: 60 kmol
Component Mole X V.P P.P = VP x X Y
Benzene 40 0.4 385 154 0.647
Toulene 60 0.6 140 84 0.363
Total : 238
At. 90oC
P = [Link]+ [Link]
P= V.P XA +V.P XB
= V.P XA +V.P (1-XA)
= 1013 XA +408 (1-X
XA)
706 = 605 XA + 408
605 XA = 352.
XA = 352/605
= 0.58
XB = 0.42
Multiple Choice Questions
01 A compound may consists of _______ phase
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
a) Only one
b) Only two
c) Not more than two
d) One or more than one
Answer (d)
02 Incorrect equation for an ideal is
a) PV = nRT
b) Pv = RT
c) PM = ρRT
d) None of the mentioned
where: P – Absolute Pressure of the gas
V – Total volume occupied by the gas
n – Number of moles of the gas
T – Absolute temperature
v – Specific molar volume
ρ – Density of the gas
Answer (d)
03 Specific molar volume for an ideal gas is
a) Volume per mass
b) Volume per molecular weight
c) Volume per mole
d) None of the mentioned
Answer (c)
04 Volumetric flow rate for a given gas can be expressed in cubic feet per second.
The above given statement is
a) Correct
b) Incorrect
c) Depends on the nature of the gas
d) None of the mentioned
Answer (a)
05 If the temperature and pressure both are made doubled then what is the volume of the
gas?
a) 16.4 m3
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
b) 38.4 m3
c) 44.5 m3
d) 85.6 m3
Answer (a)
06 Antoine equation is a relation between
a) Vapour pressure and partial pressure
b) Vapour pressure and Temperature
c) Vapour pressure and absolute pressure
d) None of the mentioned
Answer (b)
07 Correct representation of the Antoine equation is
a) ln(p*) = A-B/(C+T)
b) log(p*) = A-B/(C-T)
c) ln(p*) = A+B/(C+T)
d) log(p*) = A-B/(C+T)
Where: p* & T are Vapour pressure and Temperature respectively and A, B & C are
constants.
Answer (b)
08 The temperature at which the vapour just start to condense at a specified pressure
pressur is
a) Critical temperature
b) Boiling point
c) Dew point
d) Triple point
Answer (c)
09 At dew point the partial pressure of the is equal to the partial pressure of the volatile
liquid.
The above given statements is
a) Always correct
b) Incorrect
c) Depends on the properties of the liquid
d) None of the mentioned
Answer (b)
10 Water vapour of 5 KPa at 300 K is saturated with air in a system.
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
What is the mole fraction of air?
a) 0.952
b) 0852
c) 0.259
d) 0.291
Answer (a)
11 Water vapour of 5 KPa at 300 K is saturated with air in a system.
What is the mole fraction of vapour?
a) 0.047
b) 0.057
c) 0.067
d) 0.077
Answer (a)
Descriptive Questions
01 Write briefly about Ideal gas Law and its application?
02 Define Raoultslaw, Vapour pressure, Explain Antoine Equation?
03 Write about Vapour – Liquid Equilibrium?
Unsolved Problems
01 In the manufacture of hydrochloric acid a gas is obtained which contains 25% HCL
and 75% air by volume. This gas is passed through an absorption system in which
98% of the HCL is removed. The gas enters the system at a temperature of 120℉
120 and
a pressure of 743 mm of Hg and leaves at a temperature of 80
80℉ and a pressure of
738 mm of Hg.
a) Calculate the volume of gas leaving per 100 cu ft. eentering
ntering the absorption
apparatus.
b) Calculate the percentage composition by volume of gases leaving the
absorption apparatus.
c) Calculate the weight of HCL removed per 100 cu ft. of gas entering the
absorption apparatus.
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
02 Air is assumed to contain 79.0% Nitrogen and 21.0% Oxygen by volume. Calculate
the density in grams per litre at a temperature of 70°F and a pressure of 741 mm of
Hg.
03 Combustion gas having following molal composition are a crossed into a scrubber at
a temperature of 200°C and pressure of 743 mm of Hg, N2
N2-79.2% , O2-7.2%
7.2% , CO2=
13.6% . Water is added and gas leaving at a temperature of 740 mm of Hg with in
molal composition are N= 48.3% , O2= 4.4%, CO2= 8.3
8.3%
% , water= 39% .Calculate
volume of gases leaving the scrubber per 100ft3 entering weight of water added per
100ft3 of gas entering.
04 Calcium hypochlorite is produced by absorbing chlorine in milk of lime. A gas
produced by the Deacon chlorine process eenters
nters the absorption apparatus at a
pressure of 740 mm of Hg and a Temperature of 75℉.. The partial pressure of the
chlorine is 59 mm of Hg,, the remainder being inert gases. The gas leaves the
absorption apparatus at a temperature of 80℉ and a pressure of 743 mm of Hg with
a partial pressure of chlorine of
of0.5 mm of Hg.
A. Calculate the volume of gases leaving the apparatus per 100 ft entering.
B. Calculate the weight of chlorine absorbed, per 100 ft of gas entering.
05 It is measured to market oxygen in small cylinders having Volumes of 0.5 cu ft and
each containing 1.0 lb of oxygen. if the cylinders may be subjected to a maximum
temperature of 120°F, Calculate the Pressure for which they must be designed,
assuming the applicability
pplicability of ideal gas law?
06 The following table gives Vapour pressure of hexane and heptane
Temp 69 70 75 80 85 90 95 99.2
V.P of hexane 760 780 915 1060 1225 1405 1577 1765
V.P of Heptane 295 302 348 426 498 588 675 760
Assuming the Raoults law is invalid, use the above data to calculate mole percent of
hexane in the liquid and mole percent of hexane in the vapour. At a total pressure of
760 mm of Hg.
Plot X-Y data
07 Assuming Benzene and chloro benzene from ideal solution, Plot curves relating total
and partial pressure to mole percentage of Benzene in the solution at temp. of 90,
Rajiv Gandhi University of Knowledge Technologies
Nuzvid Campus
100,110,120 oC. Also plaot the curves realting total vapour pressure and mole
percentage of Benzene in the vapour at 90 oC and 120oC. The normal boiling point of
Benzene is 79.6oC.. Following the vapour pressure data
T 90 100 110 120 130
o
P 208 293 403 592 760
o
P 1013 1340 1744 2235 2965
Video links
01
References
01 O.A Hougen, K.M. Watson, R.A. Ragataz
Ragataz, “Chemical
Chemical Process Principles Part I
Material and Energy Balances”,
Balances Second Edition, CBS Publishers, 2001.