Chemical Engineering principles– First Year/ Chapter Thirteen

Dr. Ahmed Faiq Al-Alawy

Chapter 13
Gases, Vapors, Liquids, and Solids
 Property is meaning any measurable characteristic of a substance, such as pressure,
volume, or temperature, or a characteristic that can be calculated or deduced, such as
internal energy.
 State and Equilibrium A system will possess a unique set of properties, such as
temperature, pressure, density, and so on, at a given time, and thus is said to be in a
particular state. A change in the state of the system results in a change in at least one of its
properties.
 By equilibrium we mean a state in which there is no tendency toward spontaneous change.
When a system is in equilibrium with another system, or the surroundings, it will not change
its state unless the other system, or the surroundings, also changes.
 A phase is defined as a completely homogeneous and uniform state of matter. Liquid water
would be a phase; ice would be another phase. Two immiscible liquids in the same
container, such as mercury and water, would represent two different phases because the
liquids have different properties.

13.1 Ideal Gas Law Calculations

13.1.1 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 an ideal gas. More properly, an ideal gas is an imaginary gas that
obeys exactly the following relationship
pV = nRT …13.1
Where p = absolute pressure of the gas
V = total volume occupied by the gas
n = number of moles of the gas
R = ideal gas constant in appropriate units
T = absolute temperature of the gas
Sometimes the ideal gas law is written as

pV = RT …13.1a

Where V is the specific volume (volume per mole or mass) of the gas.

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Table 13.1 Common Standard Conditions for the Ideal Gas


System T P V
SI 273.15K 101.325 kPa 22.415 m3/kg mol
Universal scientific 0.0°C 760 mm Hg 22.415 liters/g mol
60.0°F 14.696 psia
Natural gas industry 379.4 ft3/lb mol
(15.0°C) (101.325 kPa)
American engineering 32°F 1 atm 359.05 ft3/lb mol

Example 13.1
Calculate the volume, in cubic meters, occupied by 40 kg of CO2 at standard conditions.
Solution
Basis: 40 kg of CO2

40 kg CO2 1 kg mol CO2 22.42 m3 CO2 = 20.4 m3 CO2 atS.C.

44 kg CO2 1 kg mol CO2

Example 13.2
Find the value for the universal gas constant R for the following combinations of units: For 1 g mol
of ideal gas when the pressure is in atm, the volume in cm3, and the temperature in K.

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

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…13.2

Example 13.3
Calculate the volume occupied by 88 lb of CO2 at a pressure of 32.2 ft of water and at 15°C
Solution

The final volume can be calculated via Equation 13.2 in which both R and n1/n2 cancel out:

Assume that the pressure is absolute pressure.

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Another solution
The same results can be obtained by using Eq. 13.1

The Gas Density

The density of a gas is defined as the mass per unit volume and can be expressed in kilograms per
cubic meter, pounds per cubic foot, grams per liter, or other units

Example 13.4
What is the density of N2 at 27°C and 100 kPa in SI units?
Solution

The Gas Specific Gravity

The specific gravity of a gas is usually defined as the ratio of the density of the gas at a desired
temperature and pressure to that of air (or any specified reference gas) at a certain temperature and
pressure.

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Example 13.5
What is the specific gravity of N2 at 80°F and 745 mm Hg compared to air at 80°F and 745 mm Hg?

Solution

Note: for gases at the same temperature and pressure, the specific gravity is just the ratio of the
respective molecular weights. Let A be one gas and B be another.

 A  p A   mol. wt. A   TB 
Thus sp. gr.      … 13.3
 B  pB   mol. wt. B   TA 

13.1.2 Ideal Gas Mixtures and Partial Pressure

The partial pressure of gas; i defined by Dalton, pi, namely the pressure that would be exerted by
a single component in a gaseous mixture if it existed by itself in the same volume as occupied by
the mixture and at the same temperature of the mixture is …13.4

Where p i is the partial pressure of component i . If you divide Eq. (13.4) by Eq. (13.1), you find that

…13.5

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Where yi is the mole fraction of component i . Can you show that Dalton's law of the summation of
partial pressures is true using Eq. 13.5?

…13.6

Although you cannot measure the partial pressure directly with an instrument, you can calculate the
value from Eqs. 13.5 and/or 13.6

Example 13.6
A flue gas analyzes 14.0% CO2, 6.0% O2, and 80.0% N2. It is at 400°F and 765.0 mm Hg pressure.
Calculate the partial pressure of each component.

Solution
Use Eq, (13.5) pi = pt yi
Basis: 1.00 kg (or lb) mol flue gas

Component kg (or lb) mol p (mm Hg)

CO2 0.140 107.1
O2 0.060 45.9
N2 0.800 612.0
Total 1.000 765.0

On the basis of 1.00 mole of flue gas, the mole fraction y of each component, when multiplied by
the total pressure, gives the partial pressure of that component.

13.2 Material Balances Involving Gases

The only difference between the subject matter of previous chapters and this section is that
here the amount of material flow can be specified in terms of p, V, and T rather than solely mass or
moles.
Example 13.7
The product gas analyzed 6.4% CO2, 0.1% O2, 39% CO, 51.8% H2, 0.6% CH4, and 2.1% N2. It
enters the combustion chamber at 90 oF and a pressure of 35 in. Hg, and is burned with 40% excess
air (dry) which is at 70 oF and the atmospheric pressure of 29.4 in. Hg; 10% of the CO remains
unburned. How many cubic feet of air are supplied per cubic foot of entering gas? How many cubic
feet of product are produced per cubic foot of entering gas if the exit gas is at 29.4 in. Hg and 400
o
F?
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Solution
This is a steady state problem with reaction. The system is the gases in combustion chamber.

Basis: 100 lb mol gas

The entering air can be calculated from the specified 40% excess air, the reactions for complete
combustion are

The moles of oxygen required are listed in Figure E13.7. The excess oxygen is

Total moles of air in are 244.9 + 65.1 = 310 lb mol

Degree of freedom:
 Five unknowns exit, the five products.
 You can make four element balances
 You can calculate:
 Hence the problem has zero degrees of freedom.

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Make element balances

The solution of these equations is

The total moles exiting sum to 366.6 lb mol.

If you prefer the species balances

The degrees of freedom are zero. Solution of these equations gives the same results as the element
balances, as expected.
Finally, we can convert the lb mol of air and product into the volumes requested:

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Example 13.8
Gas at 15 oC and 105 kPa is flowing through an irregular duct. To determine the rate of flow of the
gas, CO2 from a tank was passed into the gas stream. The gas analyzed 1.2% CO2 by volume before
and 3.4% CO2 by volume after, addition. The CO2 left the tank, was passed through a rotameter,
and was found to flow at the rate of 0.0917 m3/min at 7 oC and 131 kPa. What was the rate of flow
of the entering gas in the duct in cubic meters per minute?
Solution
This is an open, steady – state system without reaction. The system is the duct. Figure E13.8 is a
sketch of the process.

Assume that the entering and exit gases are at the same temperature and pressure.

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Take as a basis 1 min ≡ 0.0917 m3 of CO2 at 7 oC and 131 kPa. The gas analysis is in volume
percent, which is the same as mole percent.

We do not know F and P, but can make two independent component balances, CO2 and "other",
hence the problem has zero degrees of freedom.

Note that the "other" is a tie component. The solution of Equations (a) and (c) gives

F = 5.17 m3/min at 15 oC and 105 kPa

P = 5.288 m3/min at 15 oC and 105 kPa

Check : By Equation (b) 5.17 (0.012) + 0.1177 = (0.034)(P)

P = 5.288
The equation checks out to a satisfactory degree of precision.

Problems

1. Calculate the volume in ft3 of 10 lb mol of an ideal gas at 68°F and 30 psia.
2. A steel cylinder of volume 2 m3 contains methane gas (CH4) at 50°C and 250 kPa absolute.
How many kilograms of methane are in the cylinder?
3. What is the value of the ideal gas constant R to use if the pressure is to be expressed in atm,
the temperature in Kelvin, the volume in cubic feet, and the quantity of material in pound
moles?
4. Twenty-two kilograms per hour of CH4 are flowing in a gas pipeline at 30°C and 920 mm
Hg. What is the volumetric flow rate of the CH4 in m3 per hour?
5. What is the density of a gas that has a molecular weight of 0.123 kg/kg mol at 300 K and
1000 kPa?
6. What is the specific gravity of CH4 at 70°F and 2 atm compared to air at S.C.?
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7. A gas has the following composition at 120°F and 13.8 psia.

Component Mol %
N2 2
CH4 79
C2H6 19
(a) What is the partial pressure of each component?
(b) What is the volume fraction of each component?
8. (a) If the C2H6 were removed from the gas in problem 7, what would be the subsequent
pressure in the vessel?
(c) What would be the subsequent partial pressure of the N2?
9. A furnace is fired with 1000 ft3 per hour at 60 oF and 1 atm of a natural gas having the
following volumetric analysis: CH4: 80%, C2H6: 16%, O2: 2%, CO2: 1%, and N2: 1%. The
exit flue gas temperature is 800 oF and the pressure is 760 mm Hg absolute; 15% excess air
is used and combustion is complete. Calculate the:
(a) Volume of CO2 produced per hour.
(b) Volume of H2O vapor produced per hour.
(c) Volume of N2 produced per hour.
(d) Total volume of flue gas produced per hour.
10. A flue gas contains 60% N2 and is mixed with air to cool it. If the resulting mixture flows at
a rate of 250000 ft3/hr and contains 70% N2, what is the flow rate of the flue gas? State all
your assumptions concerning the temperatures and pressures of the gas streams.
11. Two tanks containing N2 at the following conditions sit next to each other

After the two tanks are connected and reach equilibrium, the conditions in the combined
tanks are 700 kPa and 35 oC. What was the pressure in Tank B?

Answers:
1. 1883 ft3
2. 2.98 kg
3. 1.32
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4. 28.3 m3/hr
5. 0.0493 kg/m3
6. 1.02 (lb CH4/ft3 at 70 °F and 2 atm)/ (lb air/ ft3 at S.C.)
7. N2, 0.28 psia; CH4, 10.9 psia; C2H6, 2.62 psia
8. (a) 11.12 psia at 2 ft3 and 120°F; (b) 0.28 psia at 2 ft3 and 120°F
9. (a) 2735 ft3/hr; (b) 5034 ft3/hr; (c) 22429 ft3/hr; (d) 30975 ft3/hr, all at the exit temperature
and pressure.
10. 118400 ft3/hr
11. 791 kPa.

Supplementary Problems (Chapter Thirteen):

Problem 1

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Problem 2

Problem 3

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Problem 4

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Problem 5

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Problem 6

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Problem 7

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Problem 8

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