Gas Laws

Jorge Ontaneda, PhD

Basic definitions
Properties we can measure in a gas system:

 Pressure (P)

 Volume (V)

 Number of moles (n)

 Temperature (T)
Basic definitions
System boundary

Universe
System

Surroundings
Basic definitions
Open system Closed system Isolated system

Exchange of Allows the transfer of Does not allow the

matter and energy energy but not matter transfer of either matter
or energy
Basic definitions
Extensive properties: Depend on the amount

• Mass
• Volume
• Length

Intensive properties: DOES NOT depend on the amount

• Density
• Boiling point
• Temperature
Boyle’s Law
If one assumes that n and T remain constant:
  1
𝑉∝
𝑃
Isotherms
𝑃𝑉 =𝑘 1
 

𝑃1 𝑉 1=𝑃2 𝑉 2
 
Charles’ Law
If one assumes that n and P remain constant:
Isobars
𝑉 ∝𝑇
 

  𝑉
=𝑘 2
𝑇

 𝑉 𝑉2
1
=
𝑇1 𝑇2
Gay-Lussac’s Law
If one assumes that n and V remain constant:
𝑃 ∝𝑇
 

  𝑃
=𝑘 3
Isochores 𝑇

 𝑃 𝑃2
1
=
𝑇1 𝑇 2
Avogrado’s Law
If one assumes that T and P remain constant:
𝑉 ∝𝑛
 

  𝑉
=𝑘 4
𝑛

 𝑉 𝑉2
1
=
𝑛1 𝑛 2
Ideal Gas Law
Assumptions of the Ideal Gas
 The gas consists of a large number of molecules, which are in random motion and obey Newton's

laws of motion.

 The volume of the molecules is negligible compared to the volume occupied by the gas.

 No forces act on the molecules except during elastic collisions of negligible duration.

So, when a gas behaves ideally?

 Low pressures

 High temperatures
Dalton’s Law

𝑃t =𝑃1 + 𝑃2 + 𝑃3 +…
 

𝑃t = ∑ 𝑃𝑖
 

𝑖
 Dalton’s Law
  𝑅𝑇
𝑛1
𝑃1 𝑉
=
𝑃t =𝑃1 + 𝑃2
  𝑃t
(𝑛1+ 𝑛2)
𝑅𝑇
𝑉
   
;  𝑃 𝑛1
1
=
𝑃t 𝑛1 +𝑛2
  𝑛1 𝑅𝑇 𝑛2 𝑅𝑇
𝑃t = +
𝑉 𝑉    
= ; =
  𝑅𝑇
𝑃t =( 𝑛1+𝑛 2)
𝑉
𝑃t = ∑ 𝑃𝑖
 
1=∑ 𝑥𝑖
 

𝑖 𝑖
Real Gas
 Real gas: molecules interact
with one another.
 Repulsive forces: short-range
interactions, appear when
molecules are almost in contact.
 Attractive intermolecular
forces: long-range interactions,
appear when molecules are
fairly close together (not
necessarily touching),
 Low pressures ineffective when the molecules
are far apart.
 High temperatures
Real Gas
Compressibility factor (Z) is defined as:

  𝑃 V 𝑃 𝑉´
𝑍= =
𝑛𝑅𝑇 𝑅𝑇

 Used to describe the deviation of a real gas from ideal gas behavior.

 Compressibility factor values are usually obtained by calculation

from equation of states (EoS), such as the virial equation.

 Low pressures

 High temperatures
Van der Waals Equation
 
 nb is approximately the total
  2
𝑎𝑛
( 𝑉 )
𝑃+ 2 ( 𝑉 − 𝑛𝑏 ) =𝑛𝑅𝑇 volume taken up by the
molecules themselves
 is the frequency of collisions
with the walls and the force of
 It takes into account not only each collision

the “volume of the  Coefficients a and b are

regarded as empirical
molecules” but also the
parameters.
“attraction” between them
Van der Waals Equation

  2
𝑎𝑛
( )
𝑃+ 2 ( 𝑉 − 𝑛𝑏 ) =𝑛𝑅𝑇
𝑉

 It takes into account not only

the “volume of the

molecules” but also the

“attraction” between them

Van der Waals Equation

  2
𝑎𝑛
( )
𝑃+ 2 ( 𝑉 − 𝑛𝑏 ) =𝑛𝑅𝑇
𝑉

 It takes into account not only

the “volume of the

molecules” but also the

“attraction” between them

Virial Equation of State
 
Z is expressed as an expansion as a Taylor series of either or P.

  𝐵 𝐶 𝐷
𝑍 =1+ + 2 + 3 +…  
In terms of
𝑉
´ 𝑉
´ ´
𝑉

 
  In terms of
 Virial Equation of State
  𝐵 𝐶 𝐷
𝑍 =1+ + 2 + 3 +…  
𝑉
´ 𝑉
´ ´
𝑉

 Virial coefficients (A=1, B, C, D, etc) depend on temperature

 Therefore, there may be a temperature at which Z→1

 This is the so-called Boyle temperature, TB, where the properties of the

real gas coincide with those of a perfect gas as p→0.

 When Z has zero slope as p→0 if B = 0, we can conclude that B = 0 at

the Boyle temperature