CH 8351

PROCESS CALCUALTIONS
UNIT I
Base and derived Units
Composition of mixture and solutions
Calculations of pressure, volume and temperature using ideal gas law
Use of partial pressure and pure component volume in gas calculations
Applications of real gas relationships in gas calculation

Base and Derived Units:

A measured or counted quantity has numerical value and a unit. It is essential and useful to write both the
value and the unit of each quantity appearing in an equation. A dimension is a property that can be measured such as
velocity: length/time, volume: lenth3, density: Mass/length3. Measurable units are specific values of dimensions that
have been defined by convention, custom or law. Units can be treated like algebraic variables when quantities are
added, subtracted, multiplied or divided. The numerical values of two quantities may be added or subtracted only if
the units are the same.

A system of units has the following components:

1. Base Units for mass, length, time, temperature, electrical current and ligh intensity
2. Multiple units which are defined as multiples or fractions of base units.
3. Derived units are obtained by multiplying and deviding base or multiple units. They are also obtained as
defined equivalents of compound units.
SI Units: Systeme Interantionale d’Units were put into practice at the 10 th General conference on weights and
measures in 1954 at paris. This consists of six base units.

Two supplementary units namely radian and stearadian were defined to measure planer and solid angles. Later concept
of the to quanitify ‘amount of substance’ one more base unit called mole was introduced.

CGS System:
This is almost similar to SI, the principle difference being that grams (g) and centimeters (cm) are used instead of
kilograms and meters as the base units of mass and length.
FPS system: The base units of american engineering system are foot (ft) for legth, the pound mass (lb m) for mass and
second for time. The two principle difficulties of this system are decimal system is not followed here and there is not
unit for force.
Conversion of Units:

A measured quantity can be expressed in terms of any units having the appropriate dimension. Velocity may be
expressed in ft/s, miles/h, cm/yr or any other ratio of a length unit to a time unit. The equivalence between two
expressions of the same quantity may be defined in terms of a ratio. To convert a quantity expressed in terms of one
unit to its equivalent in terms of another unit, multiply the given quantity by the conversion factor (New unit/old
Unit).
 1g 
Ex: Convert 36 mg to grams: (36mg ) x   0.036mg
 1000mg 
Imporatnt conversion Factors:

Length: 1 m = 1.093 Yard = 3.28 ft; 1 cm = 0.393 inch.

Volume: 1 m = 1000 Litres = 35.315 ft 1 Litre = 0.0353 ft3 = 0.264 US gal.
3 3

Mass: 1 Kg = 1000 gr = 2.204 lb

Density: 1 g/cm3 = 62.427 lb/ft3
Specific Voluem: 1 m3/Kg = 16.018 ft3/lb
Force: 1 N = 0.101972 Kgf
Pressure: 1 KPa = 0.01019 Kgf/cm2 = 0.145038 lbf/in2; 1 bar = 0.1 MPa = 14.695 lbf/in2 = 760 mmHg
1 torr = 1 mm Hg = 133.3234 Pa
Energy: 1 J = 0.238 Cal = 9.478 x 10-4 BTU
Power: 1 KW = 1.341 HP

Problems:
1. Convert 20 gal/hr to m3/s

We know that l liter = 0.264 gal; 10-3 m3 = 0.264 gal

1 hr = 3600 Sec
 gal  10  m  1  hr 
3 3 3
5 m
Ans: 20       2.1x10
 hr  0.264  gal  3600  sec  hr
2. Convert 9 x 108 lb/ft3 hr to gm/s cm3
We know that 1 Kg = 2.204 lb; 1000 g = 2.204 lb
1 m = 3.280 ft; 100 cm = 3.280 ft
1 hr = 3600 Sec
 lb  1000  g  3.280   ft   1  hr 
3 3
g
9 x10  3 
8
         4002.67 3
 ft hr  2.204  lb  100   cm   3600  s  cm s
3. Convert 4 g mole of Mg Cl2 to gm Moleulcar weight of MgCl2 = 24 = 35.5 x 2 = 95
We know that g mole = g mass/Mol Wt; g mass = g mole x Mole wt = 4 x 95 = 380 g
4. 2 lb mole of C3H8 to g
Molecular weight of C3H8 = (12 x 3) + (1 x 8 ) = 44 lb/lb mole
2 lb mole of C3H8 = 2 x 44 = 88 lb
We know that 2.204 lb = 1 Kg = 1000 gr
88 lb = (1000/2.204) x 88 = 39927.4 gr
5. 16 g of N2 to lb mole
Molecular weight of N2 = 28
1000 g = 2.204 lb
16 g = (2.204/1000) 16 = 0.0353 lb
lb Moles of N2 = 0.0353/28 = 1.26 x 10-3lb mole
6. 3 lb of C2H6O to g mole
2.204 lb = 1000 g
3 lb = (1000/2.204) x 3 = 1361.16 g
Molecular weight of C2H6O = (12 x 2) + (1 x 6) + (16 x 1 ) = 46
g mole of C2H6O = 1361.16/46 = 28.61 g mole
7. 100 Btu/hr ft2 oF to W/m2 oC Hint 1 deg variation in F is equivalent to 1.8 times in oC)

1 J = 9.478 x 10-4 Btu

1 hr = 3600 sec
1 m = 3.28 ft
 1 degree variation in F is equivalent to 1.8 time in degree C.
 Btu  J   o F  1 
2 2
1  hr  1  ft   3.28  J
100    4        o    175 2 o
 hrft F  Btu  9.478 x10  s  3600  m   1   C  1.8 
20
sm C
10. Check the dimensional consistency of the following empirical equation for a heat transfer coefficient:
hi  0.023G 0.8 k 0.67c 0p.33 D 0.2  0.47
Where h is the heat transfer coefficient, G is the mass velocity, k is the thermal conductivity, c p is the specific
heat, D is the diameter and µ is the absolute viscosity.

Composition of mixture and solutions:

Solutions are homogeneous mixtures of pure substances. Solutions contain two or more substances
(components) mixed together in a state of molecular dispersion. The component that forms the majority of a solution
is known as the solvent, while the other components are called the solutes. Its worth noting that the solvent itself can
be a mixture.
The quantitative composition of a solution can be expressed with:
 concentration (molar, mass and volume)
  fraction (molar, mass and volume)
 Molarity, Molality and Normality.
Unless specified otherwise, the ratio refers to the mass ratio.
Molar, weight, and volume fractions are numbered, dimensionless units most commonly expressed as a:
 percentage, (% = 1/100)
 parts-per-thousand, (‰ = 1/1 000)
 parts-per-million, (ppm = 1/1 000 000)
Symb
Physical quantity Definition Unit Description
ol

cA = Molar concentration, or just the concentration of component

Concentration c mol m-3 A, is the ratio between the amount of solute A and the
n A/V
solution volume.

γA = Mass concentration of component A is equal to the ratio

Mass concentration γ kg m-3 between the mass of solute A and the solution volume.
m A/V

σA = Volume concentration of component A is equal to the ratio

Volume concentration σ m3 m-3 between the volume of solute A and the solution volume.
V A/V
Mole fraction, or the amount fraction of component A, is
xA = equal to the ratio between the amount of solute A and the
Mole fraction x
n A/∑n i sum of amounts of all substances within the solution or
mixture.

wA = Mass fraction or weight fraction of component A is the mass

Mass fraction w ratio between the solute A and the sum mass of all
m A/∑m i
substances within the solution or mixture.

φA = Volume fraction of component A is the volume ratio

Volume fraction φ between the solute A and the sum volume of all substances
V A/∑V i
in the solution.

MA = Molality of component A is equal to the ratio between the

Molality M mol kg-1 number of moles of solute A and the mass of solvent S.
n A/m S
Molarity of component A is equal to the ratio between the
Molarity m mA=nA/V mol lit-1
number of moles of solute A and the volume of the solution.

Normality N N= m x Valency Normality is the gram equivalent weight per litre of solution.

Important laws and definitions:

Weight of the component in gr
gr mole of a component = ----------------------------------------
Molecular weight
Weight of the component in Kg
Kg mole of a component = -----------------------------------------.
Molecular weight
Individual weight of the component in the sample
Weight % of a component =[------------------------------------------------------------------------] x 100
Total weight of the sample

Individual Volume of the component in the sample

Volume % of a component =[-----------------------------------------------------------------------] x 100
Total Volume of the sample

Individual Moles of the component in the sample

Mole % of a component =[-----------------------------------------------------------------------] x 100
Total number Moles of the sample
Similarly,
Individual weight of the component in the sample
Weight Fraction of a component =[------------------------------------------------------------------------]
Total weight of the sample
 Individual Volume of the component in the sample
Volume Fraction of a component =[------------------------------------------------------------------------]
Total Volume of the sample
Individual Moles of the component in the sample
Mole Fraction of a component = [---------------------------------------------------------------------]
Total number Moles of the sample

It is to be noted that sum of the Weight fractions /Volume fractions/Mole fractions is equal to 1.

Molarity (M) is defined as the number of moles of solute per liter of solution.
molarity = moles of solute/liters of solution

Molality (m) is defined as the number of moles of solute per kilogram of solvent.
molality = moles of solute/kilograms of solvent

Normality (N) is defined as the number of mole equivalents per liter of solution:
normality = number of mole equivalents/1 L of solution
Like molarity, normality relates the amount of solute to the total volume of solution; however, normality is
specifically used for acids and bases.
8. Make the following conversions:
(a) 294 gm/lit: H2SO4 to normality
(b) 5N H3PO4 to gm/lit.
(c) 54.75 gm/lit. HCl to molarity
(d) 3M K2SO4 to gm/lit.
(e) 4.8 mg/ml CaCl2 to normality.
Solution:-
(a) 294 gm/lit H2SO4 to normality Basis: 1 lit. of solution
H2SO4 in solution = 294 gm. Valence= 2; Equivalent weight 98/2 = 49
gm – equivalents of H2SO4 = 294/49 = 6 Normality = 6/1 = 6N
(b) 5N H3PO4 to gm/lit.
Mol. Weight of H3PO4 = 98 Valence of H3PO4 = 3
Equivalent weight of H3PO4 = 98
 32.67
3
gm/lit. of solution = Normality  Equivalent weight
= 5  32.67 = 163.35
(c) 54.75 gm/lit. HCl to molarity
Basis : 1 lit. of HCl solution. Amount of HCl in it = 54.75 gm
Molecular weight = 36.
1.5
Moles of HCl = 54.75  1.5 mol. Molarity =  1.5
36.5 1
(d) 3M K2SO4 to gm/lit.
Basis: 1 lit. of solution Moles of K2 SO4 = 3  1 = 3 mol.
Mol. Wt. K2SO4 = 174 Weight of K2SO4 = 3  174 = 522 gms.
Gms/lit. of solution = 522  522 gm/lit.
1
(e) 4.8 mg/ml CaCl2 to normality.
4.8 mg/ml CaCl2 = 4.8 gm/lit. CaCl2 Basis: 1 lit. of solution.
CaCl2 in solution = 4.8 gm. Mol. Weight of CaCl2 = 111
111
48
Equivalent weight of CaCl2 =  55.5 gm-equivalent of CaCl2 = = 0.0865
2 55.5
Normality = 0.0865
 0.0865
1
9. An aqueous solution of K2CO3is prepared by dissolving 43 kg K2CO3 in 100 kg water at 293 K (20C).
Find molarity, normality and molality of solution. Take density of solution as 1.3 kg/lit.
Solution:-
Basis : 43 kg of K2CO3 and 100 kg of water
Weight of K2 CO3 solution = 43 + 100 = 143 kg.
Volume of solution = 143  110 lit.
1.3
Mol. Weight of K2CO3 = 138
Equivalent weight of K2CO3 = 138/2 = 69
Moles of K2CO3 in solution = 43/138
= 0.3116 kmol.
= 311.6 mol.
Molarity of solution = 311.6
 2.832
110
43  103
gm-equivalent of K2CO3 = 69
 623.19

Normality of solution = 623.19

110
= 5.665
Molality of solution = 311.6
100
= 0.3116.
Calculations of pressure, volume and temperature using ideal gas law:
Basic Laws:

(i). Avogadro’s Law: As constant T and P volume of gas is proportional to the number of molecules of gas.
V n

(ii). Boyle’s Law: At constant T the pressure of the gas is inversely proportional to its Volume
P 1
V

(iii). Charles Law: At constant pressure, the volume is directly proportional to the temperature.

V T

(iv). Gay – Lussac’s Law: At constant volume, the pressure of the gas is proportional to temperature

P T
The ideal gas law combines all of the above laws and gives one single expression.

PV = nRT where R is universal gas constant.

An ideal gas in one in which there are no intermolecular forces of attraction or repulsion and the actual volume
occupied by the molecules is negligible compared to the total volume occupied by the gas.

Conditions for a gas to behave as predicted by the ideal gas law:

The major ones are:

1. The molecules of an ideal gas do not occupy any space; they are infinitesimally small.
2. No attractive forces exist between the molecules so that the molecules move completely independently of each
other.
3. The gas molecules move in random, straight-line motion" and the collisions between the molecules and between the
molecules and the walls of the container are perfectly elastic.

Properties of an ideal gas:

The properties of an ideal gas are:

 An ideal gas consists of a large number of identical molecules.
 The volume occupied by the molecules themselves is negligible compared to the volume occupied by
the gas.
 The molecules obey Newton's laws of motion, and they move in random motion.
 The molecules experience forces only during collisions; any collisions are completely elastic, and take
a negligible amount of time.
NTP: Zero degree centigrade and One atmospheric pressure. At NTP molal volume occupied by one Kgmole of gas
is 22.414 m3.

STP: Standard temperature and pressure condition which varies from place to place. In India it is 250 C and 1 atm
pressure.

Amagat’s Law: If Vi is the volume of pure component i present in the mixture, total volume of the gas V is given by ,

V = ∑Vi

Dalton’s Law: If Pi is the partial pressure exerted by a single component in a mixture with the mole fraction yi then
total pressure

PT = ∑Pi and Pi = PT yi

Av. Molecular Weight = ∑ Mi Yi

Where Mi = Molecular weight of ith component and Yi = Mole fraction of the ith component.

All the components in the gas mixture occupy the total volume and hence Vi is the volume occupied by the
component i, if it is present at the pressure p and temperature T of the mixture.
 n RT 
Vi   i  Where ni is the number of moles of component i.
 p 
Here Vi is proportional to ni. That is volume % of a component in a gas mixture equals to mole% of it.

Partial pressure of component i in a mixture of gases is the pressure exerted by the component when it occupies the
same volume as that of the mixture at the same temperature.
 ni RT 
Similarly Pi    Here Pi is directly proportional to ni. That is pressure% in a gas mixture equals to mole% of
 V 
it. Hence for ideal gases pressure% = Volume% = Mole%

1. Find the value of gas constant R in ft3 atm/lbmol oR

Normal Temperature = 273.15K; 1K 1.8 oR; 273.15 K = 491.67 oR.

Normal pressure = 1 atm

 m 3  ft 3  3.28   Kgmol  1 
3

Volume 22.4136  22.4136  3       358.89 ft3/lb mol

 Kgmol  m  1   lbmol  2.205 

R = PV/T = (1 x 358.89)/491.67 = 0.730 ft3 atm/lb mol oR

2. Calculate the volume of 50 Kgs of CO2 at standard conditions.

Basis: 50 Kg of CO2

Assuming the ideal gas behaviour, 1 Kg mole  22.415 m3

50 Kgs of CO2  50/44  1.14 Kg mole  1.14 x 22.415  25.55 m3

3.. What is the weight of 1 litre of methane at NTP?

At NTP, P = 101.325 kPa; T = 273.15 K n= PV/RT
= (101.325 x 103) (1 x 10-3) /8.314 x 103 (273.15)
= 0.446 x 10-3 Kg moles

Mass of chlorine = (Kg moles) x (molecular weight) = (0.446 x 10-3)(35.5) = 1.58 x 10-3 Kgs.

4. Find the value for the universal gas constant R to match the following combination of units: For 1 g mol of
ideal gas when the pressure is in atm. the volume is in cm3 I and the temperature is in K.

5. Calculate the density of air at 2.5 atm and 45oC.

Molar volume of air V = RT/P = (8.314x103)(273.15 + 45)/2.5 (1.01325 x 105) = 10.44 m3/Kg mole.
Air is assumed to be made up of Nitrogen (0.78 Mole fraction) and Oxygen (0.22 Mole fraction)
Average Molecular weight of air = 28(0.79) + 32(0.21) = 28.84 Kg/Kg mole.
Density of the gas = Molecular weight / Molal volume = 28.84/10.44 = 2.76 Kg/m3.

In many processes going from an initial state to a final state, you will find it convenient to use the ratio of the ideal gas
laws in the respective states and thus eliminate R as follows (the subscript 1 designates initial state, and the subscript 2
designates the final state)

Problems:
1. A natural gas has the following composition by volume: CH4 = 83.5%, C2H6 =12.5%, and N2= 4%. Calculate
the following (i). Composition in mole% (ii). Composition in weight% (iii) Average molecular weight and (iv)
Density at standard conditions (Kg/m3).
3. A liquid mixture contains three components A (MW = 72), B (MW = 58) and C (MW = 56) in which A and B are
present in the ratio 1.5: 1 and the weight percent of B is 25%. The specific gravities of pure liquids are 0.67, 0.60 and
0.58 respectively for A, B and C and there is no volume change on mixing. Calculate the following,
(i). The analysis of the mixture in mole percent. (ii). The MW (Molecular Weight) of the mixture.
(iii). The volume percent of C on a B-free basis. (iv). The specific gravity of the mixture.
Use of partial pressure and pure component volume in gas calculations:
Partial pressure and vapor pressure.

The partial pressure of a component in a gaseous mixture is defined as the pressure that the component exerts when it
occupies the same volume as that of the mixture at the same temperature of the mixture. The vapor pressure of liquid
is defined absolute pressure at which the liquid and its vapor are in equilibrium at a given temperature.

1. A partial pressure of oxygen in the lungs of 100 mm Hg is adequate to maintain oxygen saturation of the
blood in a human. 1s this value higher or lower than the partial pressure of oxygen in the air at sea level?

At sea level the atmospheric pressure is 760 mm Hg.

Assuming air is a binary mixture containing nitrogen and oxygen in the mole ratio of 79 % and 21 %,
The partial pressure of Oxygen = 760 x 0.21 = 159.6 mm Hg.

Hence partial pressure of oxygen in the lungs (100 mmHg) is lower than the partial pressure of oxygen in the air at sea
level.

2. A gas mixture entering an absorber contains 20% CO2 and 80% air by volume. In the absorber, 95% CO2 is
removed. The gas enters at 60oC and 750 mm HG and leaves at 40oC and 740 mm Hg. Calculate (i). Volume of
gas leaving per 100 m3 entering the absorption apparatus.
(ii). % composition by volume of gases leaving.
(iii). Weight of CO2 removed per 100 m3 of gas entering the absorber.
3. The feed to absorption column consists of 30% H2S and 70% inerts. Only H2S is removed from the gas by
absorbing in an alkaline solution. The gas enters the absorber at 700 kPa, 350 K and leaves at 600 kPa, 300 K
containing 5% H2S. If H2S is removed at a rate of 100 Kg/hr, calculate the following:
(i). Number of moles of each component entering and leaving the system.
(ii). Cubic meters of gas entering per hour. (iii). Cubic meters of gas leaving per hour.
(iv). Percentage recovery of H2S
1. 1000 litres of a mixture of H2, N2, and CO2 at 150oC was found to have the following ratio for the partial pressures
of the gases: PH2:PN2:PCO2 is 1:4:3. If the total pressure is 2 atm absolute, calculate
(i). Mole fraction of each of these gases.
(ii). Weight percent of each of these gases.
(iii). Average Molecular weight
(iv). Weight of CO2 in Kg.
Applications of real gas relationships in gas calculation
Real Gases:

Early experimenters found that at the critical point all substances are in approximately the same state of molecular
dispersion. Consequently it was felt that their thermodynamic and physical properties should be similar. The law of
corresponding states expresses the idea that in the critical state all substances should behave alike.

Critical state (point) means for a pure component, the maximum temperature and corresponding pressure at which
liquid and vapor can coexist. 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 become identical.

One way to determine the critical state is by acoustic measurements because the speed of sound in a fluid
drops to a minimum when the fluid is in the critical state.
Point C, 310C is the highest temperature at which liquid and gaseous CO2 can coexist in equilibrium. Above 310C
only fluid exits. Hence critical temperature for CO2 is 310C and corresponding pressure is 72.9 atm (7385 kPa).
Above critical properties, all gases can be represented by ideal gas law, takes the shape of a hyperbola pV = Constant.
Critical property data are available in the literature.

A supercritical fluid is a compound in a state above its critical point. Supercritical fluids are used to replace solvents
such as trichloroethylene and methylene chloride, the emissions from which, and the contact with, have been severely
limited. For example coffee decaffeination, the removal of cholesterol from egg yolk with CO2 the production of
vanilla extract, and the destruction of undesirable organic compounds all can take place using supercritical water.
Oxidation in supercritical water has been shown to destroy 99.99999% of all of the major types of toxic agents present
in chemical weapons, which are being eliminated.

Reduced Variables: These are corrected, or normalized, conditions of temperature. Pressure, or volume, normalized
(divided) by their respective critical conditions as follows:

The law of corresponding states indicates that any compound should have the same reduced volume at the same
reduced temperature and reduced pressure so that a universal gas law might be:

Compressibility: Ideal gas law can be modified so as it can be used for real gases also by inserting an adjustable
coefficient z, the compressibility factor, a factor that compensates for the non ideality of the gas, and can be looked at
as a measure non ideality. Thus the ideal gas is turned into a real gas law, a generalized equation of state.

Compressibility Charts: We can use what is called the generalized compressibility factor z for gas calculations.
Figure shows an example of the generalized compressibility factor chart or z-factor chart. It represents Z for gases.
Equations of State: Another way of predicting p, V, n and T for real gases are by using equations of state. Ideal gas
equation itself is a simplest example of an equation of state. They can be just empirical relations selected to fit a data
set or based on the theory or combination of two.
Advantages of using an equation of state versus other prediction methods are:
1. Values of p-V-T can be predicted with reasonable error in regions where no data exist.
2. Only a few values of coefficients are needed in the equation to be able diet gas properties versus collecting large
amounts data by experiment.
3. The equations can be manipulated on a computer whereas graphics methods cannot.
Disadvantages are:
1. The form of an equation is hard to change to fit new data.
2. Inconsistencies may exists between equations for p-V-T and equations for other physical properties.
3. Usually the equation is quite complicated and may not be easy to solve for p.VI or T because of its nonlinearity T

1. Estimate the density of the chlorine gas at temperature 503 K and 15.2 MPa pressure using,
(i). Ideal gas law (ii) The van der Walls equation.