The Behavior of Gases

Dr. Sushil Kumar Sharma, M.Sc,

Ph.D (Organic Chemistry)
Assistant Professor, SHUATS,
Pyayagraj, U.P(E)
 Properties of Gases (Review)
 No definite shape
 No definite volume
 compressible
 Kinetic Molecular Theory

moving molecules well supported ideas

 Basic Kinetic Theory of Gases
1. Composed of particles like atoms
(ex: He) or molecules like (O2 and
CO2)

There are no attractive/repulsive

forces.

Lots of empty space!!

 Basic Kinetic Theory of Gases
2. Particles move in
random, constant,
straight-line motion.

Move independently
of each other.
 Basic Kinetic Theory of Gases
3. All collisions are elastic meaning
that KE is transferred without loss of
energy.

No change in kinetic energy.

Gases tend to diffuse towards areas of

lower concentration.
 Gas Pressure
 Pressure- force exerted on container
walls by particles in a gas
 Units used- kPa, atm, Torr, mmHg
 STP (Standard Temperature and
Pressure) Table A

273 K or 0°C and

101.3 kPa = 1 atm = 760 Torr (mmHg)
 Factors Affecting Pressure
Amount of Increasing amount Ex: bicycle tires,
Gas (number will increase P car tires
of moles) (and vice versa)

Temperature Increasing temp. Ex: Tires deflate

will increase P in winter
(and vice versa)

Volume Decreasing Ex: press down

volume will on a balloon and
increase P, it pops
increasing volume
decreases P
 Pressure and volume have an inverse
relationship, if temperature remains
constant.

 If volume is increased, pressure is

decreased by the same factor.
Mathematically, the product of PV is constant or PV = k

(where k is some constant).

Boyle’ Law

P1 V1 = P2 V2 = P3 V3…
Summary
 Volume and temperature have a
direct relationship, if pressure is held
constant.

 If temperature (K) is increased,

volume is increased by the same
factor.
Mathematically, the relationship of volume divided by Kelvin

temperature is constant or V/T = k.

Charles’ Law

V1 /T1 = V2 /T2 = V3 /T3 …

Summary
 Pressure and temperature have a
direct relationship, if volume remains
constant.

 If temperature (K) is increased,

pressure will be increased by the
same factor.
Mathematically, the relationship of volume divided by Kelvin

temperature is constant or P/T = k.

Gay-Lussac’s Law
P
r
e P1 /T1 = P2 /T2 = P3 /T3 …
s
s
u
r
e
Combined Gas Law Equation

P 1 V1 = P 2 V2
T1 T2
 Combined Gas Law Equation
 Steps:
 Determine which variable (if any) is kept
constant.
 Cancel those terms and remove them from
the equation (Ex: If the question says that
temperature remains constant the new
equation becomes P1V1 = P2V2).
 Plug in values that are given.
 Solve for the unknown.
 Be sure to always use temperature in
Kelvins.
 Ideal Gases vs. Real Gases
 “Ideal gases” behave as predicted
by Kinetic Molecular Theory.
 Examples: H2 and He

 Gases are most ideal at high

temperature and low pressure (also
have low mass and low polarity).
 “Real gases” deviate from ideal
behavior.
 Why?
 At low temps, gas particles
become attracted to each other
(KMT says they are not).
 Under high pressure, gases occupy
a specific volume (KMT says they
don’t).
 Avogadro’s Law

 Avogadro’s number: 6.02 x 1023

 Simply refers to the quantity of particles
found in a mole.
 At STP, 6.02 x 1023 particles of a gas
occupies 22.4 L.
 At STP, 3.01 x 1023 particles of a gas
occupies 11.2 L.
 Avogadro also
hypothesized that
equal volumes of
different gases at the
same temperature
and pressure contain
equal number of
particles (or equal
moles).
 Vapor Pressure
 In a sealed container, vapor pressure
can be measured above a liquid.

 Evaporation occurs when some

particles from the surface of a liquid
escape causing pressure to build up
above the liquid (not to be confused
with boiling).
 Factors that Increase the Rate of
Evaporation
 Heating a liquid (not to
boiling point)

 Increasing surface area

 Create air currents

(blow across the surface)
 Liquid-Vapor Equilibrium
 Some of the gas particles condense
and then we find both evaporating
and condensing occurs at the same
rate.
 Rate of Evaporation = Rate of Condensation
 Related to Boiling
 Boiling occurs when the vapor
pressure becomes equal to the
external pressure.

 At normal atmospheric pressure, we

call this normal boiling point.
 Boiling and Attractive
(Intermolecular Forces)
 Boiling occurs when heat energy
overcomes attractive forces between
molecules.

 The stronger the intermolecular forces, the

higher the boiling point.

 The weaker the intermolecular forces, the

lower the boiling point.
 Table H

Notice, increasing
temperature increases
vapor pressure.

Line drawn at 101.3 kPa

corresponds to normal
boiling point.
 Problems Related to Boyle’s Law

 An 18.10mL sample of gas is at 3.500 atm. What will be the

volume if the pressure becomes 2.500 atm, with a fixed
amount of gas and temperature?
Solution: P1V1 = P2V2
By solving with the help of Boyle’s law equation
P1V1 = P2V2
V2 = P1V1 / P2
V2 = (18.10 * 3.500 atm)/2.500 atm
V2 = 25.34 mL
 Problems Related to Charle’s Law

 A sample of carbon dioxide in a pump has a volume of

21.5 mL, and it is at 50.0 °C. When the amount of gas
and pressure remain constant, find the new volume of
carbon dioxide in the pump if the temperature is increased
to 75.0 °C.
 Solution: V1 / T1 = V2 / T2
V2 = V1T2/T1
V2 = 7,485.225/ 323.15
V2 = 23.16 mL
 Problems Related to Gay-Lussac Law
 Determine the pressure change when a constant volume of gas
at 2.00 atm is heated from 30.0 °C to 40.0 °C.
 Solution: P1 / T1 = P2 / T2
P1 = 2.00 atm
P2 =?
T1 = (30 + 273) = 303 K
T2 = (40 + 273) = 313 K
According to the Gay-Lussac law,
P∝T
P/T = constant
P1/T1 = P2/T2
P2 =( P1 T2 ) / T1
= (2 x 313) / 303
=2.06 atm
 Problems Related to Avogadro’s Law
At constant temperature and pressure, 6.00 L of a gas is known to
contain 0.975 mol. If the amount of gas is increased to 1.90 mol, what
new volume will result?
Solution: V1 / n1 = V2 / n2
V1 = 6.00 L
V2 = ?
n1 = 0.975
n2 = 1.90 mol
According to Avogadro’s law
V∝n
V/n = constant
V1 / n1 = V2 / n2
V2 = V1n2/n1
V2 = (6 x 1.90)/ 0.975 = 11.69 L
 Combined Gas Law Problem
The initial volume of the gas is 5L and final volume is 3L Calculate the final
pressure of the gas, given that the initial temperature is 273 K, the final
temperature is 200 K, and initial pressure is 25 kPa.
Solution: PiVi/Ti = PfVf/Tf
According to the given parameters,
Pi= 25 kPa
Vi = 5L, Vf = 3L, Ti = 273K, Tf = 200K
According to combined gas law,
PiVi/Ti = PfVf/Tf
Substituting in the formula, we get
25 x 5 / 273 = Pf x 3 / 200
Therefore, Pf = 30.525 kPa
Gas Law Formula Table
 van der waals equation

The equation is basically a modified version of

the Ideal Gas Law which states that gases consist
of point masses that undergo perfectly elastic
collisions. However, this law fails to explain the
behaviour of real gases. Therefore, the Van der
Waals equation was devised, and it helps us
define the physical state of a real gas.
The Van der Waals equation is an equation
relating the relationship between the pressure,
volume, temperature, and amount of real gases.
For a real gas containing ‘n’ moles, the equation
is written as

Where P, V, T, and n are the pressure, volume, temperature

and moles of the gas, respectively, and ‘a’ and ‘b’ constants
specific to each gas.
 Significance or merits of van der Waals equation
 The equation of Van der Waals can tell the behavior of
gas easily in a better and more accurate way than this
equation named equation of ideal gas.
 Equations of Van der Waals are also used and are
accurate to fluids, not just to gases.
 The pattern arrangement of the equation of Van der
Waals is in the way of a cubic equation in terms of
volume.
 The equation of cube in volume gives the three volumes.
 These three volumes are for measuring the volume at
critical temperature or below the given critical
temperature.
 Insignificance or demerits of van der Waals
equation
• The equation of Van der Waals can get correct
or accurate answers only for the real gases,
also only those which are above or at the
critical temperature.
• The gases below the critical temperature, these
gases results get accepted.
• But when gas is in the phase of transition, the
equation of this is termed as wrong or a failure
to an extent.
 The derivation of Van der Waals equation for one mole of gas
To deduce or derive the equation of Van der Waals for the volume of one
mole of a gas. We need to follow these easy steps.

This is the derivation of van der Waals equation for one mole of gas.
 critical constants and their determination

The kinetic theory of gases is a theoretical framework

that describes the behavior of gases based on the motion
of their individual particles. The critical constants of a gas
are specific thermodynamic properties that are crucial for
understanding its behavior, especially near the critical
point. The critical point is the set of conditions (critical
temperature, critical pressure, and critical volume) at
which a gas and its liquid phase become
indistinguishable.
The critical constants for a gas are: Tc, Pc and Vc
1. Critical Temperature (Tc): The highest temperature
at which a gas can exist in the liquid state. Above this
temperature, no amount of pressure can liquefy the
gas.
2. Critical Pressure (Pc): The pressure required to
liquefy a gas at its critical temperature. At pressures
above the critical pressure, the gas cannot exist in the
liquid state.
3. Critical Volume (Vc): The volume occupied by one
mole of gas at the critical temperature and pressure.
 1. Critical Temperature (Tc​):
 Determination:
• One experimental method involves studying the
vapor pressure of a substance at various temperatures.
At the critical temperature, the distinction between
the liquid and gas phases disappears. The vapor
pressure reaches a point where it can no longer be
distinguished from the critical pressure.
• The Clausius–Clapeyron equation(way of describing
a discontinuous phase transformation between two
phases of matter of a single constituent, named after
Rudolf Clausius and Benoît Paul Émile Clapeyron.)
can be useful in this context.
 2. Critical Pressure (Pc​):
Determination:
• Experimental determination of critical pressure
involves increasing the pressure on a gas while
keeping the temperature constant. At the
critical pressure, the gas and liquid phases
become indistinguishable.
• This is often observed in a phase diagram
where, at the critical point, the liquid-gas
boundary ceases to exist.
 3. Critical Volume (Vc​):
 Determination:
• Critical volume is determined experimentally by
measuring the specific volume of the gas at the
critical point.
• A common method involves studying the
behavior of the gas at different pressures and
temperatures and plotting a phase diagram. The
critical volume is the volume occupied by one
mole of the gas at the critical temperature and
pressure.
 This lecture including the following items

 Enthalpy and why it is used.

 Heat capacities and specific heats
 Relation between cv and cp
 Specific heats for ideal gases
 The first law of thermodynamics for ideal gases
 Exercises
 For Your Information
If heat is added to a material at constant pressure so that the specific
volume of the material increases from α1 to α2, the work done by a unit
mass of the material is p(α2 - α1).
as we know that:
Then the finite quantity of heat Δq added to a unit mass of the material at
constant pressure is given by :

where u1 and u2 are, respectively, the initial and final internal energies
for a unit mass of the material.
Therefore, at constant pressure,
where h is the enthalpy of a unit mass of the material,which is defined
by

Because u, p, and α are functions of state, h is a function of state.

 ENTHALPY

It is one of the state variables, and is defined as

H ≡ U + pV

The differential of H is given as

dH = dU + pdV + Vdp

This makes it possible to write the first law of thermodynamics as:

dH = dQ +Vdp (1)
 WHY USING ENTHALPY?
 The reason enthalpy is convenient to use is that for constant
pressure processes, dp = 0 and so dH = dQ.
o Since many thermodynamic processes in the atmosphere occur
at constant pressure, change in enthalpy and heat are equivalent
and are used interchangeably in such processes.
o In an isobaric (constant pressure) process, dW = dU − dH ,
which states that the work is the difference in the changes of
internal energy and enthalpy.
 From the first form of the first law, dU = dQ – pdV, we see that at
constant volume, dU = dQ.
o For constant volume processes, heat and change in internal
energy are interchangeable.
• For constant pressure processes, heat and enthalpy change are equivalent.
• For constant volume processes, heat and internal energy change are
equivalent.
 HEAT CAPACITIES AND SPECIFIC HEATS
 Heat capacity is the amount of heat Q needed to raise the
temperature of a substance T by one degree.
 Heat capacity is defined in terms of either a constant volume
process or a constant pressure process (At constant pressure, some
of the heat supplied goes into doing work of expansion and less
is available with the system )

• From the two forms of the first law (dH = dQ), and (dU = dQ), we
can show that:

so that the definitions for heat capacity can also be written as

 HEAT CAPACITIES AND SPECIFIC HEATS
• The units of heat capacity are J K−1.
• Heat capacity is an extensive property (depends on ‘amount of
matter’), its intensive counterpart is called specific heat, and is
defined as

 The units of specific heat are J K−1 kg−1.

 Heat capacities and specific heats are not constant, but are functions
of T and p.
• If a substance has higher heat capacity, then more heat has to be
added to raise its temperature.
 RELATION BETWEEN Cv and Cp

• To see the relation between Cv and Cp we start with the:

From the definition of enthalpy,

H =U + pV ,
we take the partial derivative with respect to T at constant pressure to
get:

Substituting (9) into (8) we get

The differential of U is:

RELATION BETWEEN Cv and Cp
RELATION BETWEEN Cv AND Cp

Riddles

For gases, Cp > Cv, why?

 SPECIFIC HEATS FOR IDEAL GASES
Recall that the specific heat at constant volume and the specific heat at
constant pressure was defined as:

Since the internal energy and enthalpy of an ideal gas depend only on
temperature, then for an ideal gas we don’t have to write the specific
heats as partial derivatives, but can instead use full derivatives

From the expressions for the internal energy of ideal gases,

we get that
 SPECIFIC HEATS FOR IDEAL GASES

The expression relating the specific heats at constant pressure and at

constant volume is also greatly simplified for an ideal gas. The general
expression [Eqn. (13)] becomes, for an ideal gas,
Cp-Cv=R’ (14)
which tells us that:

99% of the atmosphere is composed of diatomic molecules (N2 and

O2), and has a specific gas constant of 287.1 J-kg−1-K−1. This leads to
values of Cv and Cp of 718 J-kg−1-K−1 and 1005 J-kg−1-K−1. These
values are extremely close to the measured values for the atmosphere.
THE FIRST LAW OF THERMODYNAMICS FOR
IDEAL GASES
THE FIRST LAW OF THERMODYNAMICS FOR
IDEAL GASES