LECTURE 2- THE GAS LAWS

2.1. IDEAL AND REAL GASES

It is convenient to classify all gases into two types: (a) ideal gases, and (b) non ideal or real gases. An
ideal gas is one that obeys certain laws which will be presented shortly, while a real gas is one that obeys
these laws only at low pressures.

GENERALIZATIONS OF IDEAL GAS BEHAVIOR

Through the study of gases there have evolved certain laws or generalizations which are the starting
point in any discussion of gas behavior. These are: (a) Boyle’s law, (b) Charles’s or Gay-Lussac’s Law, (c)
Dalton’s Law of Partial Pressures, and (d) Graham’s Law of Diffusion.

2. 2. BOYLE’S LAW
Robert Boyle, (1627-91), who was an “experimental philosopher”
in the early years of the Royal Society, made a very important contribution
in developing a description of the ideal gas (also developed ideas about
vacuum, atomic nature of matter, etc.)
In 1661, he showed that to a very good approximation that for a
constant amount of gas at a fixed temperature:
1 1
𝑝𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝∝ , 𝑉∝
𝑉 𝑝
The pressure of a sample is inversely proportional to its volume,
and the volume of a sample is inversely proportional to pressure.
Boyle did thousands of experiments on air, due to the invention of
an air pump by his assistant, Robert Hooke.
Boyle and Hooke used a glass J-tube to examine the properties of
air.
Hg was poured into the column (at T) and air was trapped in the sealed end. When the pressure
exerted by the Hg was doubled, Boyle found that the volume of trapped air would reduce by half - leading to
the discovery of Boyle’s (or Mariotte’s) Law: pV = k at constant T

Isotherms: p vs V
Here are some plots depicting Boyle’s Law. Each plotted line corresponds to a different temperature,
and are known as isotherms, as they depict the other variables of the state function at a constant
temperature:

(a) For plots of p vs. V, the

isotherms are Hyperbolas
(i.e., plot of y as function of x
when xy = constant)

(b) For plots of p vs. 1/V, the

isotherms are linear

(a) (b)

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2.3 CHARLES’ LAW
Charles' law (also known as the law of volumes) is an experimental gas law which describes
how gases tend to expand when heated. It was first published by French natural philosopher Joseph Louis
Gay-Lussac in 1802, although he credited the discovery to unpublished work from the 1780s by Jacques
Charles. The law was independently discovered by British natural philosopher John Dalton by 1801, although
Dalton's description was less thorough than Gay-Lussac's.
A modern statement of Charles' law is:
At constant pressure, the volume of a given mass of an ideal gas increases or decreases by the
same factor as its temperature on the absolute temperature scale (i.e. the gas expands as the temperature
increases).
which can be written as:
𝑽∝ 𝑻
where V is the volume of the gas; and T is the absolute temperature. The law can also be usefully
expressed as follows:
𝑽𝟏 𝑽𝟐 𝑽𝟐 𝑻 𝟐
= 𝒐𝒓 = 𝒐𝒓 𝑽𝟏 𝑻𝟐 = 𝑽𝟐 𝑻𝟏
𝑻𝟏 𝑻𝟐 𝑽𝟏 𝑻 𝟏
The equation shows that, as absolute temperature increases, the volume of the gas also
increases in proportion.

Effects of Changing Temperature

The volume of a gas should extrapolate to zero near -273oC. Plots of volume and pressure as a
function of temperature, at constant pressure and volume, respectively, are shown below:

Lines of
constant
volume are
known as
isochors:

Lines of constant pressure are known Pressure falls to zero as T approaches

as isobars: notice how an infinitely
absolute zero (i.e., n molecular motion)
small V implies a temperature near -
273℃

Rationalizing Charles’ Law

As the temperature is increased, the average speed of the molecules increases, thereby increasing the
number and force of the collisions that the molecules have with the container’s walls (again, this only really
applies at low pressures).
In order to build up to the ideal gas law, we need to consider the relationship between volume and
the number of molecules.
The molar volume is the volume per mole of molecules:
Vm = V /n
For any gas, the molar volume is the same, regardless of the type of gas. So, Avogadro’s principle says
that the volume of any gas is directly proportional to the number of molecules at constant temperature and
pressure:
V = constant × n

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2.4 COMBINING THE GAS LAWS
Boyle’s Law: pV = constant, when n and T are constant
Charles’ Law: p α T, V α T, if n and either V or p are held constant
Avogadro’s Principle: V α n, at constant T and p

Single expression: pV = constant × nT = nRT

(where n is the number of moles of gas and R is the ideal, or universal, gas constant, equal to the
product of Boltzmann's constant and Avogadro's number. The temperature used in the equation of state is an
absolute temperature: in the SI system of units, kelvins; in the Imperial system, degrees Rankine.)

This is the perfect gas equation, which becomes very accurate as the pressure decreases. This is a
limiting law, which increases in validity as p → 0. A limiting law is strictly true at a particular limit.
A real gas behaves like a perfect gas in the low pressure limit: at this point, the gas constant, R, can be
determined very accurately.

standard ambient pressure and temperature (SATP):

T = 298.15 K, p = 1 bar, molar volume of gas Vm = 24.790 L mol-1
standard temperature and pressure (STP)
T = 0 oC, p = 1 atm, molar volume of gas Vm = 22.414 L mol-1

R is related to the Boltzmann constant, k: R = k x NA

where
k = 1.3806 x 10-23 J K-1 NA = 6.022 x 1023 mol-1

Surface of States

The perfect gas equation:

pV = nRT
can be represented as a three-dimensional surface of possible states, meaning that the gas cannot exist in
states not on the surface

EXAMPLE 1
A hydrogen gas thermometer is found to have a volume of 100.0 cm3 when placed in an ice-water
bath at 0°C. When the same thermometer is immersed in boiling liquid chlorine, the volume of hydrogen at
the same pressure is found to be 87.2 cm3. What is the temperature of the boiling point of chlorine?

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SOLUTION:
For hydrogen, PV = nRT, where P is pressure, V is volume, n is number of moles, R is the gas
constant, and T is temperature.
Initially:
P1 = P, V1 = 100 cm3, n1 = n, T1 = 0 + 273 = 273 K
PV1 = nRT1
Finally:
P2 = P, V2 = 87.2 cm3, n2 = n, T2 = ?
PV2 = nRT2
Note that P, n, and R are the same. Therefore, the equations may be rewritten:
P/nR = T1/V1 = T2/V2
and T2 = V2T1 / V1
Plugging in the values we know:
T2 = 87.2 cm3 x 273 K / 100.0 cm3
T2 = 238 K

ANSWER:
238 K (which could also be written as -35°C)

EXAMPLE 2
Calculate the approximate molar mass of a gas whose measured density is 3.33 g/L at 30 ○C and 780
Torr.

SOLUTION:
From the ideal gas equation, the number of moles contained in 1 L of gas is
780
𝑃𝑉 ( 𝑎𝑡𝑚) (1𝐿)
𝑛= = 760 = 0.0413 𝑚𝑜𝑙
𝑅𝑇 0.008206 𝑎𝑡𝑚 − 𝐿
( ) (393𝐾)
𝑚𝑜𝑙 𝐾
The molecular weight is therefore:
3.33 𝑔 𝒈
( ) (0.0413 𝑚𝑜𝑙) (1𝐿) = 𝟖𝟎. 𝟔
𝐿 𝒎𝒐𝒍

2.5 DALTON’S LAW OF PARTIAL PRESSURES

Different gases introduced into the same container interdiffuse or mix rapidly. Dalton’s law of
partial pressures states that at constant temperature the total pressure exerted by a mixture of gases in a
definite volume is equal to the sum of the individual pressures which each gas would exert if it occupied the
same total volume alone.
Mathematically, the pressure of a mixture of gases can be defined as the summation
𝑛

𝑃𝑡𝑜𝑡𝑎𝑙 ∑ 𝑝𝑖 𝑜𝑟 𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑝1 + 𝑝2 + ⋯ + 𝑝𝑛
𝑖=1
where 𝑝1 , 𝑝2 , … , 𝑝𝑛 represent the partial pressure of each component.
It is assumed that the gases do not react with each other.
𝑝𝑖 = 𝑃𝑡𝑜𝑡𝑎𝑙 𝑌𝑖
where 𝑌𝑖 the mole fraction of the i-th component in the total mixture of n components.

2.6 AMAGAT’S LAW

Amagat's law or the Law of Partial Volumes of 1880 describes the behaviour and properties of
mixtures of ideal (as well as some cases of non-ideal) gases. Of use in chemistry and thermodynamics,
Amagat's law states that the volume Vm of a gas mixture is equal to the sum of volumes Vi of the K component
gases, if the temperature T and the pressure p remain the same:

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 𝐾

𝑉𝑚 (𝑇, 𝑝) = ∑ 𝑉𝑖 (𝑇, 𝑝)
𝑖=1
This is the experimental expression of volume as an extensive quantity. It is named after Emile
Amagat. Both Amagat's and Dalton's Law predict the properties of gas mixtures. Their predictions are the
same for ideal gases.

Gas A Gas B Gas Mixture

T and P
+ T and P
= T and P

VA VB VA + VB = V

𝑃𝑉𝐴 = 𝑛𝐴 𝑅𝑇 𝑃𝑉𝐵 = 𝑛𝐵 𝑅𝑇 𝑃𝑉 = 𝑛 𝑅𝑇

𝑽𝑨 𝑽𝑩 𝑽 𝒏𝑨 𝑽𝑨 𝒏 𝑩 𝑽𝑩
= = 𝒕𝒉𝒖𝒔 = = 𝒚𝑨 𝒂𝒏𝒅 = = 𝒚𝑩
𝒏𝑨 𝒏𝑩 𝒏 𝒏 𝑽 𝒏 𝑽

Wherein the volume of an ideal gas mixture (V) is equal to the sum of the component volumes (Vj’s)
of each individual component in the gas mixture at the same temperature (T) and total pressure (P) of the
mixture.
However, for real (non-ideal) gases, the results differ. Dalton's Law of Partial Pressures assumes that
the gases in the mixture are non-interacting (with each other) and each gas independently applies its
own pressure, the sum of which is the total pressure. Amagat's Law assumes that the volumes of each
component gas (same temperature and pressure) are additive; the interactions of the different gases are the
same as the average interactions of the components.
The interactions can be interpreted in terms of a second virial coefficient, B(T), for the mixture. For
two components, the second virial coefficient for the mixture can be expressed as:
𝐵(𝑇) = 𝑋1 𝐵1 + 𝑋2 𝐵2 + 𝑋1 𝑋2 𝐵1,2
where the subscripts refer to components 1 and 2, the X's are the mole fractions, and the B's are the
second virial coefficients. The cross term, B1,2, of the mixture is given by:
𝐵1,2 = 0 (Dalton's Law)
𝐵1,2 = (𝐵1 + 𝐵2 )/2 (Amagat's Law).

2.7 GRAHAM’S LAW OF DIFFUSION

Different gases diffuse through a tube or escape from a container having a fine opening at different
rates dependent on the densities or molecular weights of the gases. The law governing such diffusions was
first enunciated by Graham in 1829 and bears his name. This law states that at constant temperature and
pressure the rates of diffusion of various gases vary inversely as the square roots of their densities or
molecular weights. Thus, if we let µ1 and µ2 be the rates of diffusion of two gases, and ρ1 and ρ2 be their
respective densities, then
𝜇1 √𝜌2
=
𝜇2 √𝜌1
Again, since at the same pressure and temperature both gases must have the same molar volume V m,
we have also that
𝜇1 √𝜌2 𝑉𝑚 √𝑀2
= =
𝜇2 √𝜌1 𝑉𝑚 √𝑀1
where M1 and M2 are the molecular weights of the two gases.

2.8 COMPRESSIBILITY FACTOR

The compressibility factor (Z), also known as the compression factor, is a useful thermodynamic
property for modifying the ideal gas law to account for the real gas behaviour. In general, deviations from
ideal behavior become more significant the closer a gas is to a phase change, the lower the temperature or the

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 larger the pressure. Compressibility factor values are usually obtained by calculation from equations of
state (EOS), such as the virial equation which take compound specific empirical constants as input.
Alternatively, the compressibility factor for specific gases can be read from generalized compressibility charts
that plot Z as a function of pressure at constant temperature.
The compressibility factor is defined as:
𝑝𝑉𝑚
𝑍=
𝑅𝑇
where, p is the pressure, 𝑉𝑚 is the molar volume of the gas, T is the temperature, and R is the gas
constant. In engineering applications, it may be expressed in the following way:

𝑝
𝑍=
𝑅𝜌𝑇

where, p is the pressure, ρ is the density of the gas, T is the temperature, and R is the gas constant.
For an ideal gas the compressibility factor is Z =1 per definition. In many real world applications
requirements for accuracy demand that deviations from ideal gas behaviour, i.e. real gas behaviour, is taken
into account. The value of Z generally increases with pressure and decreases with temperature. At high
pressures molecules are colliding more often. This allows repulsive forces between molecules to have a
noticeable effect, making the volume of the real gas ( Vreal) greater than the volume of an ideal gas (Videal)
which causes Z to increase above one. When pressures are lower, the molecules are more free to move. In this
case attractive forces dominate, making Z < 1. The closer the gas is to its critical point or its boiling point, the
more Z deviates from the ideal case.

EXERCISES:

1. A gas that behaves ideally has a density of 1.92 g dm–3 at 150 kPa and 298 K. What is the molar mass
of the sample?
2. A Dumas experiment to determine molar mass is conducted in which a gas sample’s P, θ, and V are
determined. If a 1.08-g sample is held in 0.250 dm3 at 303 K and 101.3 kPa: a. What would the
sample’s volume be at 273.15 K, at constant pressure? b. What is the molar mass of the sample?
3. A 0.200-dm3 sample of H2 is collected over water at a temperature of 298.15 K and at a pressure of
99.99 kPa. What is the pressure of hydrogen in the dry state at 298.15 K? The vapor pressure of
water at 298.15 K is 3.17 kPa.
4. The density of air at 101.325 kPa and 298.15 K is 1.159 g dm–3. Assuming that air behaves as an
ideal gas, calculate its molar mass.
5. The volume of a vacuum manifold used to transfer gases is calibrated using Boyle’s law. A 0.251-dm3
flask at a pressure of 697 Torr is attached, and after system pumpdown, the manifold is at 10.4
mTorr. The stopcock between the manifold and flask is opened and the system reaches an
equilibrium pressure of 287 Torr. Assuming isothermal conditions, what is the volume of the
manifold?
6. The decomposition of KClO3 produces 27.8 cm3 of O2 collected over water at 27.5 °C. The vapor
pressure of water at this temperature is 27.5 Torr. If the barometer reads 751.4 Torr, find the volume
the dry gas would occupy at 25.0 °C and 1.00 bar.
7. Balloons now are used to move huge trees from their cutting place on mountain slopes to
conventional transportation. Calculate the volume of a balloon needed if it is desired to have a lifting
force of 1000 kg when the temperature is 290 K at 0.940 atm. The balloon is to be filled with helium.
Assume that air is 80 mol % N2 and 20 mol % O2. Ignore the mass of the superstructure and
propulsion engines of the balloon.
8. It takes gas A 2.3 times as long to effuse through an orifice as the same amount of nitrogen. What is
the molar mass of gas A?
9. A gas mixture consists of 320 mg of methane, 175 mg of argon, and 225 mg of neon. The partial
pressure of neon at 300 K is 8.87 kPa. Calculate (a) the volume and (b) the total pressure of the
mixture.

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 10. A gas at 250K and 15atm has a molar volume 12% smaller than that calculated for the equation of
state of an ideal gas. Hence calculate:
(a) The compressibility factor (Z) for this temp and pressure
(b) The molar volume of the gas
11. A 423 mL sample of dry oxygen at STP is transferred to a container over water at 22° C and 738 mm
Hg. What is the new volume of the oxygen?
12. What is the molecular weight of a gas which diffuses 1/50 as fast as hydrogen?
13. If the density of hydrogen is 0.090 g/L and its rate of diffusion is 5.93 times that of chlorine, what is
the density of chlorine?
14. A 0.200 dm3 sample of H2 is collected over water at a temperature of 298.15 K and at a pressure of
99.99 kPa. What is the pressure of the hydrogen in the dry state at 298.15K? The vapor pressure of
water at 298.15K is 3.17kPa.

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