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(An Autonomous Institution Affiliated to JNTUK, AP)

rd

Class 3 Sem. - B. Tech. (Chemical Engineering)

Course Chemical Process Calculations Course Code CHEM-2403

Prepared by Mr. P. Satya Sagar, Sr. Assistant Professor

Lecture Topic Methods of expressing compositions of gas mixtures

Course Outcome CCHEM203.1 Program Outcome PO1,PO13

Duration 50 min Lecture 2 of 45 Unit I

REMEMBER UNDERSTAND APPLY ANALYSE EVALUATE CREATE

Learning Level

(Tick whichever is applicable)

1. Objectives

To learn Methods of expressing compositions of gas mixtures

2. Topic Learning Outcomes

After the completion of the class the students will able to:

a. Calculate composition of gas mixture in different methods and able

b. Calculate molar volume of component in mixture

c. Convert volume percent to mole percent and weight percent vice versa

3. Teaching Methodology

a. Chalk & Talk

4. Applications

1. Combustion calculations 2. Fertilizer industry 3.Petrochemical

industry

5. Evocation

6. Discussion

Standard Conditions

1 atm. pressure or 760 mm Hg or 29.92 inches of Hg and 0 C or 32 F By Avogadros

Hypothesis, 1 g mole of any gas under standard conditions will occupy 22.414 litres 1 lb mole of

any gas under standard conditions will occupy 359 cu.ft.

T(K) = T C + 273.16

T(R) = T F + 459.69

Ideal Gas Law

The ideal gas law states that,

PV = nRT

P = Pressure of gas

V = Volume of n moles of gas

n = Number of moles of gas

R = Gas constant

T = Absolute temperature

Using the ideal gas law (PV = nRT) and the above information one can always determine the

weight of a gas if the volume is known and vice-versa.

The molar volume of a gas

You will recall that the molar mass of a pure substance is the mass of 6.02 x 1023 (Avogadro's

number) of particles or molecular units of that substance. Molar masses are commonly expressed

in units of grams per mole (g mol1) and are often referred to as molecular weights.

As was explained in the preceding lesson, equal volumes of gases, measured at the same

temperature and pressure, contain equal numbers of molecules Standard temperature and

pressure: 273K, 1 atm

The magnitude of this volume will of course

depend on the temperature and pressure, so as

a means of convenient comparison it is

customary to define a set of conditions

T = 273K and P = 1 atm as standard

temperature and pressure, usually denoted

as STP. Substituting these values into the ideal

gas equation of state and solving for V yields a

volume of 22.414 liters for 1 mole.

Example 1

What would the volume of one mole of air be

at 20C on top of Mauna Kea, Haw'aii (altitude

4.2 km; click on picture for enlarged view) where the air pressure is approximately 60 kPa?

SOLUTION

Apply Boyle's and Charles' laws as successive correction factors to the standard sea-level

pressure of 101.3 kPa:

The standard molar volume 22.4 L mol1 is a value worth memorizing, but remember that it is

valid only at STP. The molar volume at other temperatures and pressures can easily be found by

simple proportion. The molar volume of a substance can tell us something about how much

space each molecule occupies, as the following example shows.

Example 2

Estimate the average distance between the molecules in a gas at 1 atm pressure and 0C.

SOLUTION

Consider a 1-cm3 volume of the gas, which will contain 6.021023mol1, 22,400cm3 mol1

=2.691019cm3 , 6.021023mol1, 22,400cm3 mol1 = 2.691019cm3

The volume per molecule (not the same as the volume of a molecule, which for an ideal gas is

zero!) is just the reciprocal of this, or 3.72E 20 cm3. Assume that the molecules are evenly

distributed so that each occupies an imaginary box having this volume. The average distance

between the centers of the molecules will be defined by the length of this box, which is the cube

root of the volume per molecule:

(3.72 1020)1/3 = 3.38 107 cm = 3.4 nm

Molar mass and density of a gas

The molecular weight (molar mass) of any gas is the mass, expressed in grams, of Avogadro's

number of its molecules. This is true regardless of whether the gas is composed of one molecular

species or is a mixture. For a mixture of gases, the molar mass will depend on the molar masses

of its components, and on the fractional abundance of each kind of molecule in the mixture. The

term "average molecular weight" is often used to describe the molar mass of a gas mixture.

Average molecular weight

The average molar mass of a mixture of gases is just the sum of the

mole fractions of each gas, multiplied by the molar mass of that

substance:

Expressing the composition of a gas mixture

Because most of the volume occupied by a gas consists of empty space, there is nothing to

prevent two or more kinds of gases from occupying the same volume. Homogeneous mixtures of

this kind are generally known as solutions, but it is customary to refer to them simply as gaseous

mixtures. We can specify the composition of gaseous mixtures in many different ways, but the

most common ones are by volumes and by mole fractions.

Volume fractions

From Avogadro's Law we know that "equal volumes contains equal numbers of molecules". This

means that the volumes of gases, unlike those of solids and liquids, are additive. So if a

partitioned container has two volumes of gas A in one section and one mole of gas B in the other

(both at the same temperature and pressure), and we remove the partition, the volume remains

unchanged.

We can specify the composition of this mixture by saying that the volume fraction of A is 1/3

and that of B is 2/3.

Volume fractions are often called partial volumes:

Don't let this type of notation put you off! The summation sign (Greek Sigma) simply means to

add up the v's (volumes) of every gas. Thus if Gas A is the "i-th" substance as in the expression

immediately above, the summation runs from i=1 through i=2. Note that we can employ partial

volumes to specify the composition of a mixture even if it had never actually been made by

combining the pure gases.

When we say that air, for example, is 21 percent oxygen and 78 percent nitrogen by volume, this

is the same as saying that these same percentages of the molecules in air consist of O2 and N2.

Similarly, in 1.0 mole of air, there is 0.21 mol of O 2 and 0.78 mol of N2 (the other 0.1 mole

consists of various trace gases, but is mostly neon.) Note that you could never assume a similar

equivalence with mixtures of liquids or solids, to which the E.V.E.N. principle does not apply.

Mole fractions

These last two numbers (0.21 and 0.78) also express the mole fractions of oxygen and nitrogen in

air. Mole fraction means exactly what it says: the fraction of the molecules that consist of a

specific substance. This is expressed algebraically by

Note: ,

Partial Pressure (PP) The partial pressure of a component gas that is present in a mixture of

gases is the pressure that would be exerted by that component gas if it alone were present in the

same volume and at the same temperature as the mixture.

Pure Component Volume (PCV) The PCV of a component gas that is present in a mixture of

gases is the volume that would be occupied by that component gas if it alone were present at the

same pressure and temperature as the mixture.

Dalton's law of partial pressures The ideal gas equation of state applies to mixtures just as to

pure gases. It was in fact with a gas mixture, ordinary air, that Boyle, Gay-Lussac and Charles

did their early experiments. The only new concept we need in order to deal with gas mixtures is

the partial pressure, a concept invented by the famous English chemist John Dalton (1766-1844).

Dalton reasoned that the low density and high compressibility of gases indicates that they consist

mostly of empty space; from this it follows that when two or more different gases occupy the

same volume, they behave entirely independently.

The contribution that each component of a gaseous mixture makes to the total pressure of the gas

is known as the partial pressure of that gas. Dalton himself stated this law in the simple and

vivid way shown at the left.

The usual way of stating Dalton's Law of Partial Pressures is

The total pressure of a gas is the sum of the partial pressures of its components

which is expressed algebraically as

There is also a similar relationship based on volume fractions, known as Amagat's law of partial

volumes. It is exactly analogous to Dalton's law, in that it states that the total volume of a mixture

is just the sum of the partial volumes of its components. But there are two important differences:

Amagat's law holds only for ideal gases which must all be at the same temperature and pressure.

Dalton's law has neither of these restrictions. Although Amagat's law seems intuitively obvious,

it sometimes proves useful in chemical engineering applications. We will make no use of it in

this course.

7.Mind Map:

8. Readings:

1. Hougen, Olaf A., and Kenneth M. Watson. "Chemical Process Principles-Part 1: Material

and Energy Blances." (1948).

2. Himmelblau, David Mautner, and James B. Riggs. Basic principles and calculations in

chemical engineering. FT Press, 2012.

3. Bhatt, B. I., and S. M. Vora. Stoichiometry:(si units). Tata McGraw-Hill Pub. Co., 1996.

4. http://chemwiki.ucdavis.edu/Textbook_Maps/General_Chemistry_Textbook_Maps/Map

%3A_Chem1_(Lower)/06._Properties_of_Gases/6.3%3A_Dalton's_Law

9. Questions:

Remember:

1) State the fallowing laws ; Amagats law , Daltons law,

2) Define the fallowing : Partial pressure , Molar volume , Mole fraction, Pure component

volume

Understand:

1) Derive the expression for mole fraction of single compound from Daltons law of partial

pressures

2) Write short notes on standard conditions.

Apply:

1) A natural gas has the following composition, all gures being in volumetric per cent:

Methane CH4 83.5, Ethane C2H6 12.5, Nitrogen N2 4.0. Calculate composition in mole

percent and weight percent, average molecular weight.

10. Key Words:

Mole fraction

Partial pressure

Molar volume

Mole fraction

Pure component volume

Amagats law

Daltons law

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