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Ideal Gases
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• Ideal Gases
• Dalton’s Law of Partial Pressure
• Raoult’s Law
• Henry’s Law
• Antoine Equation
- Simplest and most widely used relationship is the ideal gas equation of state
which is applicable to many problems involving gases at low pressures.
where,
𝑷𝑽 = 𝒏𝑹𝑻 𝑷 = 𝒂𝒃𝒔𝒐𝒍𝒖𝒕𝒆 𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆 𝒐𝒇 𝒂 𝒈𝒂𝒔
or 𝑽 𝑽 = 𝒗𝒐𝒍𝒖𝒎𝒆 𝒗𝒐𝒍𝒖𝒎𝒆𝒕𝒓𝒊𝒄 𝒇𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒐𝒇 𝒈𝒂𝒔
𝒏 𝒏 = 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 𝒎𝒐𝒍𝒂𝒓 𝒇𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒈𝒂𝒔
𝑷𝑽 = 𝒏𝑹𝑻 𝑹 = 𝒕𝒉𝒆 𝒈𝒂𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕, 𝒘𝒉𝒐𝒔𝒆 𝒗𝒂𝒍𝒖𝒆𝒔 𝒅𝒆𝒑𝒆𝒏𝒅𝒔 𝒐𝒏 𝒕𝒉𝒆 𝒖𝒏𝒊𝒕𝒔 𝒐𝒇 𝑷, 𝑽, 𝒏 𝒂𝒏𝒅 𝑻
𝑻 = 𝒂𝒃𝒔𝒐𝒍𝒖𝒆 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒈𝒂𝒔
• The equation maybe written as: 𝑷𝑽 = 𝑹𝑻
where,
𝑉 𝑉
𝑉 = 𝑜𝑟
𝑛 𝑛
It is the specific volume of the gas.
𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑥 𝑣𝑜𝑙.
• The gas constant R has units of
𝑚𝑜𝑙𝑒 𝑥 𝑡𝑒𝑚𝑝.
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33 1
Standard Temperature and Pressure
For an ideal gas at an arbitrary temperature T and pressure P,
𝑃𝑉 = 𝑛𝑅𝑇
for the same ideal gas at a specified reference temperature 𝑇𝑠 and pressure
𝑃𝑠 (also known as STP), we may write the equation as:
𝑃𝑠𝑉 = 𝑅𝑇𝑠
System 𝑻𝒔 𝑷𝒔 𝑽𝒔 𝒏𝒔
SI 273K 1 atm 0.022415 𝒎𝟑 1 mol
Solution:
𝑃𝑉 𝑇
=𝑛
𝑃𝑠𝑉 𝑇𝑠
𝑚 1100 𝑘𝑔
𝑛= = ℎ = 19 𝑘𝑚𝑜𝑙/h
𝑀𝑊 58.1 𝑘𝑔
𝑘𝑚𝑜
𝑙
𝑇𝑃
⇒ 𝑉 = 𝑛𝑉𝑠
𝑇𝑠 𝑃𝑠
22.4 𝑚3 633 𝐾 1 𝑎𝑡𝑚
⇒ 𝑉 = 19 𝑘𝑚𝑜𝑙 = 𝟑𝟐𝟗 𝒎𝟑/𝒉
𝑘𝑚𝑜𝑙 273 𝐾 3 𝑎𝑡𝑚
Example 5.2-3 (Felder)
Ten cubic feet of air at 70℉ and 1.00 𝑎𝑡𝑚 is heated to 610℉ and compressed
to 2.50 𝑎𝑡𝑚. What volume does the gas occupy in its final state?
Solution:
𝒏 (𝒍𝒃 − 𝒎𝒐𝒍 𝒂𝒊𝒓) 𝒏 (𝒍𝒃 − 𝒎𝒐𝒍 𝒂𝒊𝒓)
Process
𝑉1 = 10𝑓𝑡3 𝑉2 =? 𝑓𝑡3
𝑇1 = 70℉ 𝑇2 = 610℉
𝑃1 = 1 𝑎𝑡𝑚 𝑃2 = 2.5 𝑎𝑡𝑚
𝑃2𝑉2 𝑛𝑅𝑇2
⇒ =
𝑃1𝑉1 𝑛𝑅𝑇1
𝑃1 𝑇2
𝑉2 = 𝑉1
𝑃2 𝑇1
= 𝟖. 𝟎𝟖 𝒇𝒕𝟑
SOLUTION
At S.C. (state 1)
𝑝 = 33.91 𝑓𝑡 𝐻2𝑂
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3314
IDEAL GAS MIXTURES
- Suppose 𝑛𝐴 moles of substance A, 𝑛𝐵 moles of B, 𝑛𝑐 moles of C and so one,
are contained in a volume V at a temperature T and total pressure P
𝒑𝑨 𝒏𝑨
= = 𝒚 𝑨 (𝑡𝑒 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑖𝑛 𝑡𝑒 𝑔𝑎𝑠)
𝑷 𝒏
or 𝒑𝑨 = 𝒚𝑨𝑷
𝒑𝑨 + 𝒑𝑩 + ⋯ = (𝒚𝑨 + 𝒚𝑩 + ⋯ )𝑷 = 𝑷
𝒑𝒊 = 𝑯𝒊𝒙𝒊
where,
𝑝𝑖 is the pressure in the gas phase of the dilute component at equilibrium at
some temperature, 𝑥𝑖 is the liquid phase mole fraction and
Note: 𝑯𝒊 values can be found in
𝐻𝑖 is the Henry’s law constant several handbooks
𝑝𝑖
Note that: = 𝑦𝑖 ⇒ 𝐻 𝑖 𝑥 𝑖
𝑝𝑡 𝑜 𝑝𝑡 𝑜
𝑡 𝑡
𝒑𝒊 𝑯𝒊𝒙𝒊
⇒ 𝒚𝒊 = =
𝒑𝒕𝒐𝒕 𝒑𝒕𝒐𝒕
Henry’s law
• Gas solubility increases as the partial pressure of a gas above the liquid
increases.
• Some of the CO 2 molecules come into contact with the surface of the water
and dissolve into the liquid. Now suppose that more CO 2 is added to the
space above the container, causing a pressure increase.
• More CO 2 molecules are now in contact with the water and so more of them
dissolve. Thus the solubility increases as the pressure increases.
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3321
When carbonated beverages are packaged, they are done so under high
CO2 pressure so that a large amount of carbon dioxide dissolves in the liquid.
Immediately, bubbles of CO2 rapidly exit the solution and escape out of the
top of the open bottle.
If the bottle is left open for an extended period of time, the beverage becomes
“flat” as more and more CO2 comes out of the liquid.
Take for example 𝐶𝑂2 dissolved in water at 40℃ for which the value of H is
69,600 𝑎𝑡𝑚/𝑚𝑜𝑙 fraction. (The large value of H shows that 𝐶𝑂2(𝑔) is only
sparing soluble in water).
For example, if 𝑦𝐶𝑂2 = 4.2 𝑥 10−6, the partial pressure of the 𝐶𝑂2 in the gas
phase is
𝑝𝐶𝑂2 = 69,600 4.2 𝑥 10−6 = 0.29 𝑎𝑡𝑚
• Raoult’s law states that a solvent’s partial vapor pressure in a solution (or mixture)
is equal or identical to the vapor pressure of the pure solvent multiplied by its mole
fraction in the solution.
• Where,
𝑝𝑠𝑜𝑙𝑢𝑡𝑖𝑜n = vapor pressure of the solution
𝑥𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = mole fraction of the solvent
𝑝 𝑠𝑜𝑙𝑣𝑒𝑛𝑡∗ = vapor pressure of the pure solvent
What is the Importance of Raoult’s law?
Assume that we have a closed container filled with a volatile liquid A. After
some time, due to evaporation, vapour particles of A will start to form. Then as
time passes, the vapour particles of A will be in dynamic equilibrium with the
liquid particles (on the surface). The pressure exerted by the vapour particles
of A at any particular temperature is called the vapour pressure of A at that
temperature.
• Now imagine we are adding another liquid B (solute) to this container. This will
result in B particles occupying the space between A particles on the surface of the
solution.
• For any given liquid there are a fraction of molecules on the surface which will have
sufficient energy to escape to the vapour phase.
• Since now we have a lesser number of A particles on the surface, the number of
vapour particles of A in the vapour phase will be lesser. This will result in lower
vapour pressure of A.
• Now if we assume that B is volatile as well, we will have lesser number of B
particles in the vapour phase as compared to pure liquid B.
• This new pressure (partial pressure) of each (A and B) is given by Raoult’s
law and depends on the concentration of each component in the liquid
phase.
𝑝𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑝𝑠𝑜𝑙𝑣𝑒𝑛𝑡∗𝑥𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑝𝐴∞ 𝑥𝐴
𝒑𝑨 = 𝒑𝑨∗𝒙𝑨
And similarly for B,
𝒑𝑩 = 𝒑𝑩∗𝒙𝑩
𝑩
𝒍𝒐𝒈𝟏𝟎 𝒑∗ =𝑨−
𝑻+𝑪
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3329
GAS-LIQUID SYSTEMS
- Systems containing several components, of which only one is capable of
existing as a liquid at the process conditions, are common in industrial
processes.
- The mole fraction of water in the gas phase, 𝑦𝐻2𝑂, increases, and hence so
does the partial pressure of water, 𝑝𝐻2𝑂 = 𝑦𝐻2𝑂𝑃.
- Eventually, however, the amount of water in the gas phase is such that the rate
at which water molecules enter the gas phase approaches zero, and thereafter
no change occurs in the amount or composition of either phase.
- The gas phase is then said to be saturated with water – it contains all the
water it can hold at the system temperature and pressure – and the water in
the gas phase is referred to as a saturated vapor.
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3331
RELATIVE VOLATILITY
• Vapor liquid equilibrium calculations can sometimes be simplified through
the use of the quantity called the relative volatility, which may be defined in
terms of the following depiction of vapor and liquid phases in equilibrium:
𝒚𝒊/𝒙𝒊
𝜶𝒊𝒋 =
𝒚𝒋/𝒙𝒋