The Gas Laws

All gases generally show similar behaviour when the conditions are normal. But with a slight
change in physical conditions like pressure, temperature or volume they show a deviation. Gas
laws are an analysis of this behaviour of gases.
Boyle’s law
It states that the volume of a given mass of a gas is inversely proportional to its pressure at
constant temperature.
Mathematically, Boyle's law can be stated as:
PV = k Pressure multiplied by volume equals some constant k
where P is the pressure of the gas, V is the volume of the gas, and k is a constant.
The equation states that the product of pressure and volume is a constant for a given mass of
confined gas and this holds as long as the temperature is constant. For comparing the same
substance under two different sets of conditions, the law can be usefully expressed as:
P1V1= P2V2
This equation shows that, as volume increases, the pressure of the gas decreases in proportion.
Similarly, as volume decreases, the pressure of the gas increases.
Graphical representation of Boyle’s law

Charles’s law
It states that the volume of a given mass of a gas is directly proportional to its absolute
temperature at constant pressure
V/T=k
V is the volume of the gas,
T is the temperature of the gas (measured in kelvins), and
k is a non-zero constant.

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Example
A balloon is filled to a volume of 2.20L at a temperature of 22oC. The balloon is then heated to a
temperature of 71oC. Find the new volume of the balloon.
V1=2.20L
T1=22oC=295K
T2=71oC=344K
V2=V1×T2/T1
V2=2.20L×344K/295K=2.57L

Gay-Lussac's Law
It states that the pressure of a given mass of gas is directly proportional to its absolute temperature
when the volume is kept constant. As a gas is cooled at constant volume, its pressure continually
decreases until the gas condenses to a liquid. It is a special case of the ideal gas law.
𝑃
Mathematically, it can be written as 𝑇 = 𝑘
where:
P is the pressure of the gas,
T is the temperature of the gas (measured in kelvins)
k is a constant.
This law holds true because temperature is a measure of the average kinetic energy of a
substance; as the kinetic energy of a gas increases, its particles collide with the container walls
more rapidly, thereby exerting increased pressure.

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For comparing the same substance under two different sets of conditions, the law can be written
𝑃1 𝑃2
as: as 𝑇1 = 𝑇2

Gay-Lussac's law, Charles's law, and Boyle's law form the combined gas law. These three gas
laws in combination with Avogadro's law can be generalized by the ideal gas law.
The relationship between the pressure and absolute temperature of a given mass of gas (at
constant volume) can be illustrated graphically as follows.

Examples
1. The pressure of a gas in a cylinder when it is heated to a temperature of 250K is 1.5 atm. What
was the initial temperature of the gas if its initial pressure was 1 atm.
Given,
Initial pressure, P1 = 1 atm
Final pressure, P2 = 1.5 atm
Final temperature, T2 = 250 K
As per Gay-Lussac’s Law, P1T2 = P2T1
Therefore, T1 = (P1T2)/P2 = (1x250)/(1.5) = 166.66 Kelvin.
2. At a temperature of 300 K, the pressure of the gas in a deodorant can is 3 atm. Calculate the
pressure of the gas when it is heated to 900 K.
Initial pressure, P1 = 3 atm

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Initial temperature, T1 = 300K
Final temperature, T2 = 900 K
Therefore, final pressure (P2) = (P1T2)/T1 = (3 atmx900K)/300K = 9 atm.
Kinetic theory and ideal gases
All gases are modeled on the assumptions put forth by the Kinetic Theory of Matter, which
assumes that all matter is made up of particles (i.e. atoms or molecules); there are spaces between
these particles, and attractive forces become stronger as the particles converge. Particles are in
constant, random motion, and they collide with one another and the walls of the container in which
they are enclosed. Each particle has an inherent kinetic energy that is dependent upon temperature
only.
A gas is considered ideal if its particles are so far apart that they do not exert any attractive forces
upon one another. In real life, there is no such thing as a truly ideal gas, but at high temperatures
and low pressures (conditions in which individual particles will be moving very quickly and be
very far apart from one another so that their interaction is almost zero).
Ideal Gas Law Equation
The Ideal Gas Equation is given by:
PV=nRT
The four variables represent four different properties of a gas:
-Pressure (P), often measured in atmospheres (atm), kilopascals (kPa), or millimeters
mercury/torr (mm Hg, torr)
-Volume (V), given in liters
-Number of moles of gas (n)
-Temperature of the gas (T) measured in degrees Kelvin (K)
The ideal gas equation enables us to examine the relationship between the non-constant
properties of ideal gases (n, P, V, T) as long as three of these properties remain fixed.
For the ideal gas equation, the product PV is directly proportional to T. This means that if the
gas’ temperature remains constant, pressure or volume can increase as long as the
complementary variable decreases; this also means that if the gas’ temperature changes, it may
be partly due to a change in the variable of pressure or volume.

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Colligative properties
Colligative properties are those properties of solutions that depend on the ratio of the number of
solute particles to the number of solvent particles in a solution, and not on the nature of the
chemical species present.
Anomalous colligative properties
Anomalous colligative properties are colligative properties that deviate from the ideal colligative
behavior.
Boiling point elevation
The boiling points of solutions are higher than that of the pure solvent. This effect is directly
proportional to the molality of the solute.
Freezing point depression
The freezing points of solutions are all lower than that of the pure solvent. The freezing point
depression is directly proportional to the molality of the solute.
Osmotic pressure
The osmotic pressure of a solution is the pressure difference needed to stop the flow of solvent
across a semipermeable membrane. The osmotic pressure of a solution is proportional to the
molar concentration of the solute particles in solution.
Vapor pressure lowering
The vapor pressure of a solvent in a solution is always lower than the vapor pressure of the pure
solvent. The vapor pressure lowering is directly proportional to the mole fraction of the solute.
Henry’s Law
Henry’s law is a gas law which states that the amount of gas that is dissolved in a liquid is
directly proportional to the partial pressure of that gas above the liquid when the temperature is
kept constant. The constant of proportionality for this relationship is called Henry’s law constant
(usually denoted by ‘kH‘). The mathematical formula of Henry’s law is given by:
P ∝ C (or) P = kH.C
Where,
-‘P’ denotes the partial pressure of the gas in the atmosphere above the liquid.
-‘C’ denotes the concentration of the dissolved gas.
-‘kH’ is the Henry’s law constant of the gas.
Factors affecting Henry’s law constant
-The nature of the gas
-The nature of the solvent
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-Temperature & pressure
Therefore, different gases have different Henry’s laws constant in different solvents, as
illustrated graphically below.

Limitations of Henry;s law

Raoult’s Law
Raoult’s law states that a solvent’s partial vapour pressure in a solution (or mixture) is equal or
identical to the vapour pressure of the pure solvent multiplied by its mole fraction in the solution.
Mathematically, Raoult’s law equation is written as;
Psolution = ΧsolventP0solvent
Where,
Psolution = vapour pressure of the solution
Χsolvent = mole fraction of the solvent
P0solvent = vapour pressure of the pure solvent

Energetics
Energetics is the scientific study of energy movement and storages under change. It may refer
to:
-Thermodynamics
-Bioenergetics

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-Energy flow
Chemical energy is the energy of chemical substances that is released when they undergo
a chemical reaction and transform into other substances.
Heat of Formation
The heat of formation is the change of enthalpy when one mole of a compound is formed from
its constituent elements. This is called standard heat of formation when it is given for the
formation of substances at their standard states. The standard pressure is 105 Pa (1 bar).
However, there is no defined standard temperature. Hence, the heat of formation is given for a
constant pressure. The symbol for the standard heat of formation is ΔHf°. It can be calculated
using the following equation.

According to this equation, the standard heat of formation is equal to the difference between the
sum of the standard enthalpies of formation of the product and the standard enthalpies of
formation of reactants.
Heat of Reaction
The heat of reaction is the net amount of energy that should be added or released during a
chemical reaction. It is the change in enthalpy in a chemical reaction that occurs at a constant
pressure. The heat is either added or released in order to keep all the reactants at a constant
temperature. It is measured per mole of a substance. When this is defined for the standard state, it
is known as standard enthalpy of reaction. The standard state is the pure substance at 1 bar
pressure and at a relevant temperature.

If the value of the heat of reaction is a positive, it indicates that the reaction is endothermic (in
which the heat is absorbed from outside). But if the value of the heat of reaction is a negative, it
indicates that the reaction is exothermic (in which heat is given off).

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Example
Calculate the enthalpy change for the combustion of acetylene (C2H2).
Given:
ΔHºf CO2 = -393.5 KJ/mol
ΔHºf H2O=-241.8 KJ/mol
ΔHºf C2H2 =+227 KJ/mol
ΔHºf O2 = 0.00 KJ/mol
Equation
2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(g)
Enthalpy of products
4(-393.5) + 2(-241.8)=(-1574) + (-483.6)
= -2057.6 KJ
Enthalpy of reactants
2(+227) + 5(0.00)=454+0.00
=454 KJ
Enthalpy change
ΔHº = Vp ΔHºf(products) - Vr ΔHºf(reactants)
= -2057.6 – (+454)
= -2511.6 KJ
Hess' law states that the change of enthalpy in a chemical reaction is the same regardless of
whether the reaction takes place in one step or several steps, provided the initial and final states
of the reactions and products are the same.
Examples
(a)Cgraphite + O2 → CO2 (g) ;(ΔH = −393.5 kJ/mol) (direct step)
(b)Cgraphite + 1/2 O2 → CO (g) ; (ΔH = −110.5 kJ/mol)
(c)CO (g) +1/2 O2 → CO2 (g); (ΔH = −283.02 kJ/mol)
Reaction (a) is the sum of reactions (b) and (c), for which the total ΔH = −393.5 kJ/mol which is
equal to ΔH in (a).
The difference in the value of ΔH is 0.02 kJ/mol which is due to measurement errors.

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Applications
Hess' law is useful in the determination of enthalpies of the following:
1. Heats of formation of unstable intermediates like CO(g) and NO(g).
2. Heat changes in phase transitions and allotropic transitions.
3. Lattice energies of ionic substances by constructing Born–Haber cycles if the electron
affinity to form the anion is known.
4. Electron affinities using a Born–Haber cycle with a theoretical lattice energy
Born Haber Cycle
Born Haber cycle is a cycle of enthalpy change of process that leads to the formation of a solid
crystalline ionic compound from the elemental atoms in their standard state and of the enthalpy
of formation of the solid compound such that the net enthalpy becomes zero.
Example
Born Haber cycle of sodium chloride NaCl
The heat of formation of sodium chloride (ΔHf0) from the sodium metal and chlorine gas can be
experimentally measured.
The processes or steps in the formation of sodium chloride are-
1. Solid sodium atom sublimes to gaseous atom by absorbing heat energy (∆Hsub).
Na (s) → Na (g),
Sublimation energy ΔHsub = + 107kJ/mol
2. Gaseous sodium atom absorbs the ionization energy to release one electron and forms gaseous
sodium ion.
Na(g) → Na+(g) + 1e– ,
Ionization energy ∆HIE = +502kJ/mol
3. Diatomic gaseous chlorine breaks into two individual atoms by absorbing bond energy, such
that each chlorine atom absorbs half of the bond energy of chlorine molecule.
Cl2(g) → 2Cl(g)
Bond dissociation energy of chlorine = +121kJ/mol
4. Chlorine atom accepts an electron to form chloride ion and releases energy equivalent to
electron affinity.
Cl(g) + 1e– → Cl– (g)
Electron affinity = ∆HEA = -355kJ/mol

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5. Gaseous sodium ion and gaseous chloride ion combine to form solid sodium chloride
molecule and releases energy equivalent to lattice energy.
Na+(g) + Cl– (g) → Na+ Cl– (s)
Lattice energy = ∆HLE
Summation of enthalpy of all the processes from, steps, give the net enthalpy of formation of
solid crystalline sodium chloride from sodium and chlorine in their standard conditions of solid
and gas respectively. This should be equal to the experimentally measured enthalpy of formation
of solid sodium chloride.
The enthalpies are represented as a cycle in the figure.

Lattice energy of the sodium chloride solid = U = ΔHf0 – (ΔHsub + ∆HIE + ½ ∆Hdis + ∆HEA).
ΔHf0 = - 411
= -411 -107 -502 -121 +355
= – 786kJ/mol

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