CHARACTERISTICS OF GASES

• Different gaseous substances may have very different chemical properties but they
Gas laws are straightforward mathematical expressions that relate the observable behave quite similarly as far as their physical properties are concerned
properties of gases—were among the first quantifications of chemistry, dating from the − The noble gases (He, Ne, Ar, Kr, Xe) are all monatomic gases
1600s, a time when the ideas of alchemy ruled. Gas laws provided the first clue that − The H2, N2, O2, F2, and Cl2 are diatomic gases
quantity, how much, is important in understanding nature. • All gases are composed entirely of nonmetallic elements and all have simple
molecular formulas and, therefore, low molar masses
OBJE CTIVES • Substances that are solids or liquids under ordinary conditions can also exist in
1. Know the standard conditions of temperature and pressure (STP) gaseous state which are often referred to as vapors
2. Understand that absolute zero on the Kelvin scale is the temperature at which all • Gases volume are changeable
atomic and molecular motion stops − Expand to fill its container
3. Describe the relationships among pressure, volume, temperature, and amount of − Compress when pressure is applied
gas, and the limitations of each • Gases form homogeneous mixtures with each other regardless of the identities or
4. Distinguish between Boyle’s law, Charles’ law, Gay-Lussac’s law, Avogadro’s law, relative proportions of the component gases
the combined gas law, the ideal gas law, Dalton’s law, and Graham’s law. − Characteristic properties of gases arise because the individual molecules
5. Apply the gas laws when solving stoichiometry problems involving gaseous are relatively far apart
materials
6. Calculate gas densities, standard molar volumes, molecular weights, and formulas States of Gases
of gaseous substances from measured properties of gases The physical state of a substance is defined by its physical properties. The variables needed
7. Describe molecular motion, diffusion, and effusion of gases to define the physical condition or state of a gas are:
1. Volume, V 3. Temperature, T
Properties of gases, liquids, and solids are readily understood in terms of the behavior of 2. Number of moles, n 4. Pressure, P
their component atoms, ions, and molecules. The characteristic properties of the three
distinct forms of matter are summarized in the table below. Each substance is described by an equation of state, which correlates the variables
describing that state. For example, for a perfect gas:
TABLE 1. Properties of the States of Matter 𝑷 = 𝒇 (𝑻, 𝑽, 𝒏) =
𝒏𝑹𝑻
R is constant
𝑽
Volume is the three-dimensional space inside the container holding the gas. In other
words, the volume of the gas is simply the volume of the container it is contained.
𝑽𝒈𝒂𝒔 = 𝑽𝒄𝒐𝒏𝒕𝒂𝒊𝒏𝒆𝒓
• The SI unit for volume is the cubic meter, 𝐦𝟑 . A more common and convenient
unit is the liter, 𝐋. 𝟏 𝐋 = 𝟏 𝐝𝐦𝟑 and 𝟏 𝐦𝐋 = 𝟏 𝐜𝐦𝟑

Amount of substance is tricky. As we’ve already learned, the SI unit for amount of
substance is the mole, mol. Since we can’t count molecules, we can convert measured
mass (in g) to the number of moles, 𝒏, using the molecular or formula weight of the gas.
• By definition, one mole of a substance contains approximately 6.022 x 1023
particles of the substance.

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Temperature is the measurement of heat. Gases, at room temperature, have a lower
boiling point than things that are liquid or solid at the same temperature.
• T determines in which direction energy will flow as heat when two samples are
placed in contact through thermally conducting walls
− energy flows from the sample with the higher T to the sample with the
lower T
• ALL CALCULATIONS involving gases should be made after converting the Celsius
to Kelvin temperature.
− 𝐊 = 𝟐𝟕𝟑. 𝟏𝟓 + ℃
𝟓 𝟗
− ℃= (℉ − 𝟑𝟐) and ℉ = ℃ + 𝟑𝟐
𝟗 𝟓
Pressure is defined as the force the gas exerts on a given area of the container in which
it is contained.
− 𝐏=
𝐅 (a) (b)
𝐀
• The SI unit for pressure is the Pascal, Pa. Figure 1. The (a) barometer and (b) open-end manometers
𝐤𝐠 𝐍
− 𝟏 𝐏𝐚 = 𝟏 = 𝟏
𝐦∙𝐬 𝟐 𝐦𝟐
− If the levels in the two arms of the tube are the same, the enclosed gas has the same
• A related unit sometimes used to report pressures is the bar which equals 10- Pa
pressure as the atmospheric pressure: 𝑷𝐠𝐚𝐬 = 𝑷𝐚𝐭𝐦 .
− 1 atm = 760 mm Hg = 760 Torr = 1.01325 x 105 Pa = 101.325 kPa
− If the pressure of the enclosed gas is less than the atmospheric pressure, the mercury
is forced toward the direction of the enclosed gas. Hence, 𝑷𝐠𝐚𝐬 < 𝑷𝐚𝐭𝐦 and 𝑷𝐠𝐚𝐬 =
ATMOSPHERIC PRESSURE AND THE BAROMETER 𝑷𝐚𝐭𝐦 − 𝑷𝐡 .
• Molecules that make the atmosphere don’t pile up in thin layer at Earth’s surface − If the pressure of the enclosed gas is greater than the atmospheric pressure, the
because gas particles have such tiny masses that their kinetic energies override mercury is push towards the atmosphere. That is, 𝑷𝐠𝐚𝐬 > 𝑷𝐚𝐭𝐦 and 𝑷𝐠𝐚𝐬 = 𝑷𝐚𝐭𝐦 + 𝑷𝐡 .
the gravitational forces
− Gravity does operate and it causes the atmosphere as a whole to press EXERCISE 1
down on Earth’s surface, creating an atmospheric pressure
1. Suppose two equal-sized rooms are connected via an open doorway, but one room
• Atmospheric pressure - pressure exerted by the atmosphere on the Earth’s is warmer than the other. How is this possible? Which room would have more air
surface. Note that the atmospheric pressure decreases with increasing altitude. molecules?
• Standard atmospheric pressure - typical pressure at sea level. 2. A geochemist heats a limestone (CaCO3) sample and collects the CO2 released in
• Standard Temperature and Pressure (STP): T = 273 K, P = 1 atm. an evacuated flask attached to a closed-end manometer. After the system comes
to room temperature, 𝛥ℎ = 291.4 mm Hg. Calculate the CO2 pressure in torrs,
• Evangelista Torricelli (invented barometer) proved that atmosphere has weight atmospheres, and kilopascals.
− Barometer - device used for atmospheric pressure measurement. It is
made from an inverted glass tubing of more than 760 mm in length. The 3. What would be the height of the column if the external pressure was 101 kPa and
tube is filled with mercury and the height of the mercury column is water ρ = 1.00 g⁄cm3 was used in place of mercury?
proportional to the atmospheric pressure.
− Manometer - device used to measure the pressure of enclosed gases
whose pressures are near the atmospheric pressure.

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THE DIFFERENT GAS LAWS NOTE: Guillaume Amonton was the first to empirically determine the relationship between
P and T of a gas (⁓1700) and Joseph Louis Gay-Lussac determined the relationship more
Gas Laws are equations that express the relationships among P, T, V, and n of gases.
precisely (⁓1800)
1. Boyle’s Law (Robert Boyle): Pressure - volume relationship
5. Combined Gas Laws
At constant temperature, the volume of a fixed quantity of gas is inversely proportional
to the pressure. P1V1 P2V2
1
At constant n =
At constant T and n: V ∝ and PV = constant T1 T2
P
Hence, 𝑷𝟏 𝑽𝟏 = 𝑷𝟐 𝑽𝟐 EQUATION OF STATE
The general form of an equation of state is
2. Charles’ Law (Jacques Charles): Temperature - volume relationship
At constant pressure, the volume occupied by a fixed amount of gas is directly 𝑷 = 𝒇(𝑻, 𝑽, 𝒏)
proportional to the absolute temperature. This equation tells us that, if we know the values of T, V, and n for a particular substance,
𝑉 then the pressure has a fixed value.
At constant P and n: VT and = constant
𝑇
𝑽𝟏 𝑽𝟐
Hence, =
𝑻𝟏 𝑻𝟐 The Ideal Gas/Perfect Gas Equation of State

Note that the temperature to be used in the calculations must be absolute (in K). Ideal-gas equation is made from combining the relationships of the three prior gas law
That is, T = 273 + C. 1
Boyle’s Law: V Charles’ Law: VT
3. Avogadro’s Law (Amadeo Avogadro): Quantity - volume relationship
P
Avogadro’s hypothesis: Equal volume of gases at the same temperature and pressure Avogadro’s Law: Vn
contain equal number of molecules. nT RnT
V V=
Avogadro’s law: The volume of gas maintained at constant temperature and pressure
P P
is directly proportional to the number of moles of the gas.
Ideal gas - hypothetical gas whose P, V, and T behavior are completely described by the
𝑉 ideal gas equation.
At constant T and P: Vn and = constant
𝑛 Ideal gas equation PV = nRT
where: R = 0.0821 L·atm / mol·K
𝑽𝟏 𝑽𝟐
Hence, = P = Pressure (atm)
𝒏𝟏 𝒏𝟐
T = Temperature (K)
The same volume of any gas, say 10 mL, be it H2, He, O2, NH3, and so on, at the same n = mole of gas (mol)
temperature and pressure, contain the same number of molecules. At STP (T = 273 K V = Volume (L)
and P = 1 atm) for a mole of gas, V = 22.4 L. The value of R will depend on the units of measurements of P and V. In terms of the
variables involved, R must be of the form
4. Amonton’s law or Gay-Lussac’s Law: 𝑷𝑽 (𝐟𝐨𝐫𝐜𝐞⁄𝐚𝐫𝐞𝐚) ∙ 𝑽
𝑹 = = = 𝐟𝐨𝐫𝐜𝐞 ∙ 𝐥𝐞𝐧𝐠𝐭𝐡 ∙ 𝑲−𝟏 ∙ 𝒎𝒐𝒍−𝟏 = 𝐞𝐧𝐞𝐫𝐠𝐲 ∙ 𝑲−𝟏 ∙ 𝒎𝒐𝒍−𝟏
P1 P2 𝒏𝑻 𝒎𝒐𝒍 ∙ 𝑲
At constant P and T =
T1 T2 Various units of R are required for different purposes, and some of the most often used
values of R are given in Table 2.

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 TABLE 2. Numerical Values of R in Various Units EXERCISE 2
8.314 51 J K–1 mol–1 SI unit 1. A sample of a gas occupies 360 mL under a pressure of 0.750 atm. If the temperature
0.082 057 atm dm K 3 –1
mol –1
Commonly listed as 0.0821 L atm K –1
mol –1 is held constant, what volume will the sample occupy under a pressure of 1.00 atm?

8.314 51 x 10 erg K mol

7 –1 –1
Answer:
1.987 19 cal K–1 mol–1
0.083 145 bar dm3 K–1 mol–1 2. At 0oC and 5.00 atm, a given sample of a gas occupies 75.0 L. The gas is compressed
to a final volume of 30.0 L at 0oC. What is the final pressure of the gas?
*In SI the volume is expressed in cubic decimeters (dm3). The more familiar unit, the liter, is
now defined as 1 dm3.
Answer:

surface in Figure 2 is a plot of the pressure of a fixed amount of perfect gas against its 3. A sample of N2 exerts a pressure of 0.988 atm and occupies 12.3 L when its
volume and thermodynamic temperature as given by the ideal equation. temperature is 450 K. Assuming constant pressure, what volume will the gas occupy
at 300 K?

Answer:

4. At what T will a 10.0 L gas at constant pressure be brought to if the same gas originally
occupied 3000 cm3 at 27oC?

Answer:

Figure 2. A region of the 𝑃, 𝑉 , 𝑇 surface of a fixed amount of perfect gas. The points forming
the surface represent the only states of the gas that can exist. Sections through the surface at
constant T give the isotherms, sections at constant P give the isobars, while sections at constant 5. Two identical cylinders of N2 contain the same weight of N2. The temperature of one
V give the isochores. cylinder is 20oC and the other is 100oC. If the pressure of the one at 20oC is 1520 mm
Hg, what is the pressure of the other cylinder?
• standard ambient temperature and pressure (SATP) means 298.15 K and 1bar (i.e.
exactly 105 Pa) Answer:
− standard temperature and pressure (STP) is 0oC and 1 atm
• molar volume, 𝑉m = 𝑉/𝑛 of a perfect gas at SATP is 24.789 dm3 mol−1
− the molar volume of a perfect gas at STP is 22.414 dm3 mol−1.

6. In a laboratory, 200 cm3 of O2 gas is collected at a pressure of 73 cm Hg and

temperature of 30oC, compute the volume of the O2 gas under standard conditions.

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 GAS MIXTURES AND PARTIAL PRESSURES
Answer:
Dalton’s Law of Partial Pressures (John Dalton)
In a mixture of gases at certain temperature, the total pressure exerted by the mixture
equals the sum of pressures that each would exert if it were present alone.

Partial pressure (𝑷𝒊 ) - pressure exerted by a particular component 𝒊 of a mixture of

gases.
7. A sample of gas occupies 400 mL at STP. What volume will the sample occupy at 71oC
and 2.50 atm? For example, for a gaseous mixture of three components (𝒊 = 3) at same temperature:

Answer:
n1 RT n 2 RT n3 RT
P1 = ; P2 = ; and P3 =
V V V

Pt = P1 + P2 + P3
8. Calculate the pressure of one mole of an ideal gas which occupies 12.0 L at 25oC. n1 RT n2 RT n3 RT
Pt = + +
Answer: V V V
RT
Pt = (n1 + n2 + n3 ) since nt = n1 + n2 + n3
V
RT
9. A gas is contained in 50.0 L under 8.0 atm of pressure and at 20oC. How many moles Pt = nt
of gas are there in the container?
V
The total pressure at constant temperature and volume is determined by the total number
Answer: of moles (𝒏𝐓 ).

Partial pressure and mole fractions

n1
The mole fraction of gas 1 is given by: x1 =
ntotal
n1 RT nt RT
and the partial and total pressures are: P1 = and Pt =
V V
n1 RT
P1 n
= V = 1 = x1
Pt nt RT nt
V
Hence, P1 = x1 Pt

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EXERCISE 3 APPLICATIONS OF THE IDEAL GAS LAW
1. From data gathered by Voyager 1, scientists have estimated the composition of the Gas densities and molar mass
atmosphere of Titan, Saturn’s largest moon. The total pressure on the surface of Titan • The higher the molecular mass and pressure of a gas, the denser is the gas.
is 1220 torr. The atmosphere consists of 82 mol percent N2, 12 mol percent Ar, and • Hot gases tend to be less dense than cool gases. Denser gases will lie below that of
6.0 mol percent CH4. Calculate the partial pressure of these gases. less dense gases.
Answer: 𝑃H2 = 1220 torr (0.82) = 1,000.4 torr = 1.0 x 103 torr
𝑃Ar = 1220 torr (0.12) = 146.4 torr = 1.5 x 102 torr
PV = nRT
𝑃CH4 = 1220 torr (0.060) = 73.2 torr = 73 torr P n
= Multiply the molecular weight, M to both sides.
1220 torr RT V
P n m
2. A sample of 5.0 g He gas, 2.0 g H2 gas and 10.0 g water vapor exert a pressure of 0.5 = Recall that n = m and d = .
atm at 25C. Calculate the mole fraction of each gas, the partial pressure of each gas RT V V
and the volume occupied by the mixture. P m
Mole fraction, 𝒙 = =d
RT V
Answer:
𝑛He = 5.0 g / 4.003 g/mol = 1.249 He: 1.249 / 2.794 = 0.4470 = 0.45
𝑛H2 = 2.0 g / 2.02 g/mol = 0.9901 H2: 0.9901 / 2.794 = 0.3544 = 0.35 P
d=
𝑛H2 O = 10.0 g / 18.02 g/mol = 0.5549 H2O: 0.5549 / 2.794 = 0.1986 = 0.20 RT
𝑛total = 2.794
Volumes of Gases in Chemical Reaction
𝑃He = 0.4470 (0.5 atm) = 0.2235 atm = 0.2 atm The coefficients in a balanced chemical equation tell us the relative amounts (in moles) of
𝑃H2 = 0.3544 (0.5 atm) = 0.1772 atm = 0.2 atm reactants and products in a reaction.
𝑃H2O = 0.1986 (0.5 atm) = 0.0993 atm = 0.1 atm • The general form for these types of calculations is: volume A → amount A (in
moles) → amount B (in moles) → quantity of B (in desired units).
V = nRT / P = 2.794 mol (0.08206 L-atm/mol-K) (298 K) / 0.5 atm • In cases where the reaction is carried out at STP, we can use the molar volume at
= 136.7 L STP (22.4 L = 1 mol) to convert between volume in liters and amount in moles.
= 1 x 102 L
Collecting Gases over Water
When a gas is collected over water, the total pressure or atmospheric pressure is equal to
the sum of the pressures of the gas and the water vapor.
Patm = Pgas + PH 2O

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EXERCISE 4 DIFFUSION AND EFFUSION OF A GAS
1. What is the density (g/L) of CCl4 vapor at 714 torr and 125 C? Effusion - the escape of gas molecules through a tiny hole.
Answer: Diffusion - the spread of one substance throughout a space or throughout a second
𝐦 𝒎 substance.
𝐏𝐕 = 𝐧𝐑𝐓 = ∙ 𝐑𝐓 since 𝝆 = Thus,
𝐌𝐌 𝑽

Graham’s Law (Thomas Graham)

𝐏 𝐌𝐌
𝝆= = The effusion and diffusion rates of a gas are inversely proportional to the square root of its
𝐑𝐓 molar mass.
1
2. The safety air bags in automobile are inflated by nitrogen gas generated by the rapid Rate 
decomposition of sodium azide, NaN3: 
2 NaN 3 ( s ) → 2 Na( s ) + 3N 2 ( g ) 𝒓𝟏
𝟑𝑹𝑻
𝑴 𝑴
If an air bag has a volume of 36.0 L and is to be filled with nitrogen gas at a pressure For gases 1 and 2:
𝒓𝟐
= √ 𝟑𝑹𝑻𝟏 = √𝑴𝟐
𝟏
𝑴𝟐
of 1.15 atm at a temperature of 26.0C, how many grams of NaN3 must be
decomposed? If we let two gases travel at the same time, the distance traveled by the gas can be related
Answer: to their molar masses.

EXERCISE 5
1. Arrange the following gases in order of increasing rate of diffusion: CO, NO 2, HF, H2S,
CO2.
Answer: NO2 < CO2 < H2S < CO < HF
Molar masses: CO = 28.01, NO2 = 46.01, HF = 20.01, H2S = 34.08, CO2 = 44.01

2. An unknown gas composed of homonuclear diatomic molecule effuses at a rate that is

only 0.355 times that of O2 at the same temperature. What is the identity of the
3. A sample of KClO3 is partially decomposed producing O2 that is collected over water. unknown gas?
The volume of gas collected is 0.250 L at 26oC and 765 torr of total pressure. How Answer:
many moles of O2 are collected? How many grams of KClO3 were decomposed? PH2O 𝒓𝐗 𝟐 𝑴𝐎𝟐 𝟎.𝟑𝟓𝟓 𝒓𝐎𝟐 𝟑𝟐.𝟎𝟎 𝐠⁄𝐦𝐨𝐥 𝟑𝟐.𝟎𝟎 𝐠⁄𝐦𝐨𝐥
(26°C) = 25.21 torr = √𝑴 ↔ = √ ↔ (𝟎. 𝟑𝟓𝟓)𝟐 =
𝒓𝐎𝟐 𝐗𝟐 𝒓𝐎𝟐 𝑴𝐗𝟐 𝑴𝐗𝟐
Answer:
𝟑𝟐. 𝟎𝟎 𝐠⁄𝐦𝐨𝐥
𝑴𝐗 𝟐 = = 𝟐𝟓𝟑. 𝟗𝟐 𝐠/𝐦𝐨𝐥
(𝟎. 𝟑𝟓𝟓)𝟐

Atomic Mass = 253.92 / 2 = 126.96. Therefore, the unknown gas is I2.

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ADDITIONAL EXERCISES 12. A large flask is evacuated and found to weigh 134.567 g. It is then filed to a
pressure of 735 torr at 31 C with a gas of unknown molar mass and then weighed.
1. Explain how the perfect gas equation of state arises by combination of Boyle’s law,
Its mass is 137.456 g. The gas is then filled with water and again weighed, its
Charles’s law, and Avogadro’s principle.
mass is now 1067.9 g. Assuming that the ideal gas equation applies, what is the
2. A 1.00 L sample of gas at 760 torr is compressed to constant temperature. molar mass of the unknown gas? Given ρ(H2O) = 0.997 g/mL.
Calculate the final pressure if the initial volume was doubled.
13. A study of the effects of certain gases on the plant growth requires a synthetic
3. Calculate the temperature at which a 2.00 L sample of gas at 27 C would occupy atmosphere composed of 1.5 mol % of CO2, 18.0 mol % of O2, and 80.5 mol % of
3.00 L if its pressure were changed from 1.00 atm to 800 torr. Ar.
a. Calculate the partial pressure of O2 in the mixture if the total pressure of the
4. The density of oxygen is 1.43 g/L at STP. Determine the density of oxygen at 17
atmosphere is to be 745 torr.
C and 800 torr.
b. If this atmosphere is to be held in a 120 L space at 295 K, how many moles
5. Which of the following, if any, contains the greatest number of N atoms? of O2 are needed?
a. 22.4 L N2 gas at STP
14. How many L of NH3(g) at 850 C and 5.00 atm required to react with 1.00 mol of
b. 1.00 mol of NH4Cl
O2(g)?
c. 6.02 x 1023 molecules of NO2
4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g)
6. A 1.00 L vessel containing 1.00 g H2 gas at 27 C is connected to 2.00 L vessel
15. A sample of 0.0500 mol of ammonia gas had a volume of 235 mL. The temperature
containing 88.0 g CO2 gas, also at 27 C. When the gases are completely mixed,
and pressure were held constant and some ammonia was removed from the
what are the partial pressures and total pressure in atm?
sample. Its new volume was 175 mL. How many grams of ammonia was removed?
7. A 15.00 L vessel containing 5.65 g H2 gas at 27 C is connected by means of a
16. What volume of H2 will combine with 22 L Cl2(g) to form HCl(g)? What volume of
valve to a 6.00 L vessel containing 5.00 g oxygen gas. After the valve is opened
HCl(g) will be formed? Assume the same temperature and pressure for all gases.
and the gas is allowed to mix, what will be the partial pressure of each gas and
the total pressure at 27 C? 17. Into a 5.00 L container at 18 C are placed 0.200 mol H2, 20.0 g CO2, and 14.0 g
O2. Calculate the total pressure in the container and the partial pressure of each
8. Calcium metal reacts with hydrochloric acid to yield hydrogen and calcium chloride.
gas.
Write a balance chemical equation for the reaction. Determine the volume of
hydrogen gas at 1.00 atm pressure and 18 C produced from the reaction of 12.2 18. Compute the relative rate of effusion of H2 and CO through a fine pinhole.
g of calcium with excess hydrochloric acid.
19. A large natural gas storage tank is arranged so that the pressure is maintained at
9. A certain saturated hydrocarbon effuses about as half as fast as methane. What is 2.20 atm. On a cold day in December when the temperature is -15 C, the volume
the molecular mass of this hydrocarbon? of the gas in the tank is 28500 ft3. What is the volume of the same quantity of gas
on a warm July day when temperature is 31 C?
10. An impure sample contains Al and an unreactive material. A sample weighing 5.00
g is analyzed by its reaction with HCl according to the following equation: 20. The density of a gas composed only of carbon and fluorine is 5.61 g/L at 22 C and
2 Al(s) + 6 HCl(aq) → 3 H2(g) + 2 AlCl3(aq) 748 torr. If the gas is 17.40% carbon, find the molecular formula of this gas.
If 4.16 L of H2(g) collected over water at 25 C and 0.845 atm is produced, what
is the % Al in the sample? The vapor pressure of water at 25 C is 23.8 torr.
11. Consider He (4 g/mol) and O2 (32 g/mol). Which gas will diffuse faster and how
much?

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