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101 Gases

Gases have variable density that depends on pressure, temperature, and molar mass. The ideal gas law (PV=nRT) describes the macroscopic behavior of gases and relates these variables. Deviations from ideal behavior occur at high pressures/low temperatures when intermolecular forces are significant. Gas laws and the kinetic molecular theory provide a microscopic understanding of gas behavior in terms of particles in random motion.

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88 views

101 Gases

Gases have variable density that depends on pressure, temperature, and molar mass. The ideal gas law (PV=nRT) describes the macroscopic behavior of gases and relates these variables. Deviations from ideal behavior occur at high pressures/low temperatures when intermolecular forces are significant. Gas laws and the kinetic molecular theory provide a microscopic understanding of gas behavior in terms of particles in random motion.

Uploaded by

Qaz Zaq
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Gases

Variable Density
Solids and liquids have a definite volume, thus they have a fixed density at a given temperature
Gases have a variable density at a given temperature
Pressure and temperature and molar mass determine density for a gas
Density is directly proportional to pressure and to molar mass
Density and temperature are inversely proportional

Gas Laws Overview


Describe macroscopic behavior of gases volume, temperature, pressure (and mol number)

Combined Gas Law P V / T = constant P1 V1 / T1 = P2 V2 / T2


P and V inversely proportional
V and T directly proportional
P and T directly proportional

Avogadros Law - V & n


V and n directly proportional [n = mol number]
Applicable to stoichiometry of gas phase reactions

Ideal Gas Law PV/T=nR PV=nRT PV/nT=R


R = 0.08206 Latmmol1K1 = 62.37 Ltorrmol1K1

Gas Law Calculations


Solving for dynamic conditions Solving for static conditions
Initial and final values given Three values given
Usually for two variables Can use ideal gas law
Can use combined gas law
Examples:
Calculate the new volume of a 5.0 L balloon when the pressure drops from 1.0 atm to 0.90 atm.
P1 V1 = P2 V2 [T is constant]
(1.0 atm)(5.0 L) = (0.90 atm) V2
V2 = 5.6 L

Calculate the initial pressure of a piston containing 2.5 mL of air if the final volume and pressure are 7.5
mL and 0.30 atm, respectively.

P1 V1 = P2 V2 [T is constant]
P1 (2.5 mL) = (0.30 atm)(7.5 mL)
P1 = (0.30 atm)(7.5 mL) / (2.5 mL) = 0.90 atm
Calculate the final volume of a 5.0 L balloon if the temperature is raised from 300 K to 600 K.
V1 / T1 = V2 / T2 [P is constant]
5.0 L / 300 K = V2 / 600 K
V2 = (5.0 L)(600 K) / (300 K) = 10 L

Calculate the final temperature if the pressure in a tank drops from 20.0 atm to 8.0 atm. Initial
temperature is 300 K.
P1 / T1 = P2 / T2 [V is constant]
20.0 atm / 300 K = 8.0 atm / T2
T2 = (8.0 atm)(300 K) / (20.0 atm) = 120 K

Calculate the volume of a balloon containing 2.00 mol of gas with P = 1.00 atm and T = 300 K.
PV=nRT
(1.00 atm)(V) = (2.00 mol)( 0.08206 Latmmol 1K1)(300 K)
V = (2.00 mol)( 0.08206 Latmmol1K1)(300 K) / (1.00 atm) = 49.2 L

Calculate the number of moles in a cylinder containing 20.0 L of gas at 298 K and a pressure of 3.00 atm.
PV=nRT
(3.00 atm)(20.0 L) = n (0.08206 Latmmol1K1)(298 K)
n = (3.00 atm)(20.0 L) / (0.08206 Latmmol1K1)(298 K) = 2.45 mol

Calculate the temperature of a cylinder holding 5.00 mol of gas with P = 6.00 atm and V = 22.5 L.
PV=nRT
T = (6.00 atm)(22.5 L) / [(5.00 mol)( 0.08206 Latmmol 1K1)] = 329 K

Calculate the molar volume of a gas with P = 750 mmHg and T = 295 K.
PV=nRT
(750 mmHg / 760 mmHgatm1)(V) = (1.00 mol)( 0.08206 Latmmol1K1)(295 K)
V = (1.00 mol)( 0.08206 Latmmol1K1)(295 K) / (0.95 atm) = 24.5 L

Calculate the molar volume of a gas at STP. Standard T = 273 K and standard P = 1 atm.
PV=nRT
(1 atm)(V) = (1.00 mol)( 0.08206 Latmmol1K1)(273 K)
V = (1.00 mol)( 0.08206 Latmmol1K1)(273 K) / (1 atm) = 22.4 L

Molar volume at STP is 22.4 L for an ideal gas.


This knowledge generally allows calculations that use only simple gas laws.
Other Applications of the Ideal Gas Law
The ideal gas law can be rearranged to show the relationship between gas density and molar mass.

n/V=P/RT n=m/M d = m / V = PM / R T

M =dRT/P M=mRT/PV

Of course, at STP these become: d = M / 22.4 Lmol 1

Examples:
Calculate the density of butane (C4H10) at 0C and 1.00 atm.

M = 58.14 gmol 1
d = P M / R T = (1.00 atm)(58.14 gmol 1) / (0.08206 Latmmol 1K 1)(273.15 K)
d = 2.59 gL1

Calculate the molar mass of a gas with a density of 1.18 g L 1 at 25.0C and 1.00 atm.

M =dRT/P
M = (1.18 gL1) (0.08206 Latmmol 1K 1)(298.15 K) / (1.00 atm)
M = 28.9 gmol 1

Daltons Law of Partial Pressures PTotal = P1 + P2 + P3 + P1 = X1 PTotal


Total pressure is sum of partial pressures in a mixture of gases
The partial pressure of a component in a gas mixture is the product of mole fraction and total pressure

Vapor Pressure
Small amount of liquid evaporates to form vapor over a liquid and exerts a vapor pressure.
Thus, for gases collected by bubbling through water
PTotal = Pgas + Pwater Vapor pressure increases with temperature.

Water T(C) P(mmHg) T(C) P(mmHg)


0 4.6 60 149.4
10 9.2 70 233.7
20 17.5 80 355.1
30 31.8 90 525.8
40 55.3 100 760.0
50 92.5
Examples:
Calculate the partial pressure of oxygen in a scuba tank filled with heliox (helium and oxygen mixture).
The partial pressure of helium is 600 mmHg and the total pressure is 760 mmHg.

P = P1 + P2
760 mmHg = 600 mmHg + P2
P2 = 160 mmHg

A sample of acetylene is collected over water at a temperature of 20C. Total pressure is 500.0 mmHg.
Calculate the partial pressure of acetylene.

P = P1 + P2
500.0 mmHg = 17.5 mmHg + P2
P2 = 482.5 mmHg

Calculate the partial pressure (in mmHg) of O2 in air that has a total pressure of 0.985 atm and contains
20.95% O2.
PO2 = (0.2095)(0.985 atm)
PO2 = 0.206 atm
PO2 = (0.206 atm)(760 mmHgatm1) = 157 mmHg

Calculate the partial pressure (in mmHg) of He in air that has a total pressure of 0.995 atm and contains
5.24 ppm He.
PHe = (5.24106)(0.995 atm)(760 mmHgatm1)
PHe = 3.96103 mmHg

Kinetic Theory of Gases


Explains macroscopic behavior of gases volume, temperature, and pressure.
[Quantum mechanical and relativistic effects are negligible.]

1. Gases consist of a statistically large number of particles with finite mass.


2. Particles are in constant, random motion.
[Average kinetic energy of particles directly proportional to absolute temperature].

3. Elastic collisions between particles and walls. [Conservation of energy]


4. Intermolecular forces between particles are negligible.
5. Total particle volume negligible relative to container. [Large intermolecular spacing]

For real gases at different temperatures and pressures:


Intermolecular forces may not be negligible
Particle volume may not be negligible

Thus, real gases may deviate from ideal behavior


High pressure and/or low temperature lead to non-ideal behavior
At extremes, gas may condense into liquid
Nitrogen boils at 77 K [Liquid air at about T = 200 C]
Van der Waals Equation
Accounts for non-ideality using two constants that depend on the identity of the gas

Grahams Laws of Effusion and Diffusion


Effusion process by which individual gas molecules flow through holes in a container without
intermolecular collisions

Diffusion particles moving from an area of high concentration to an area of low concentration
Rate of effusion (diffusion) proportional to inverse square root of molar mass
Denser gases (higher molar mass) diffuse and effuse more slowly

Henrys Law and Gas Solubility


Gas solubility is directly proportional to the partial pressure of the gas
Henrys law constant depends on solute, solvent, and temperature
[Not universal like ideal gas constant.]

Background and Reference Information


Pressure = Force / Area DRY AIR 78.08% N2 0.93% Ar
Pressure is omni-directional 20.95% O2 0.03% CO2
Atmospheric pressure referenced at sea level

Common Units 1 atm = 760 mmHg = 14.7 psi

= 101.325 kPa = 29.92 inHg

= 1013.25 mb (millibar)

Temperature Average Kinetic Energy


Absolute temperature is directly proportional to average kinetic energy of the gas particles
TK = TC + 273.15 generally, can use: TK = TC + 273

Hemoglobin and Gas Transport


Partial pressure of O2 in air ~160 mmHg and in alveoli ~100 mmHg
Partial pressure of CO2 in air ~40 mmHg and in alveoli ~45 mmHg

CO2 present in blood is primarily in form of bicarbonate ion, HCO 3


Historical development of gas laws and kinetic molecular theory
NB: many discoveries were made independently by two scientists; attribution can be controversial

Barometer invented [1643, Torricelli]


Air pump invented [1652, Otto van Guericke]
Manometer invented [1661, Christian Huygens]
Mercury thermometer invented [1714, Daniel Fahrenheit]

Boyles Law [1662, Pressure and Volume]


Volume of a gas is inversely proportional to its pressure (at constant temperature)
Amontons Law [1702, Pressure and Temperature]
Pressure of a gas is directly proportional to its absolute temperature
Charles Law [1787-1802, Volume and Temperature]
Volume of a gas is directly proportional to its absolute temperature
Daltons Law [1801, Partial Pressures]
Total pressure of a mixture of gases is the sum of the partial pressures of the components
Henrys Law [1803, Solubility of Gases]
At constant temperature, the solubility of a gas in some liquid is directly proportional to the partial
pressure of that gas in equilibrium with that liquid

Gay-Lussacs Law [1809, Volumes in Reactions]


Law of combining volumes volumes of reactants and products are ratio of small integers
Avogadros Law [1811, Volume and Mol Number]
Two gas samples with equal volume contain equal number of particles (same mol number)
Grahams Laws [1831, Diffusion or Effusion]
Rate of effusion (velocity) inversely proportional to the square root of molar mass
Consequence of definition of kinetic energy (EK=mv2)
Ideal gas law [1834, Clapeyron; 1857, Clausius (from kinetic theory)]
Pressure, volume, temperature, and mol number (number of particles) related by constant
Combined gas law (for constant mol number) useful variant for closed systems
Van der Waals equation [1873, corrections for real gases]
Correction to pressure term and volume term

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