Lecture 1:

Gas Laws and Kinetic

Molecular Theory
 Thermodynamic “Universe”

System
Boundary

System

Surroundings
 Types of Systems
Water vapor

Heat Heat

Open System Closed System Isolated System

Allows exchange of Allows exchange Permits neither
matter and energy of energy only matter nor energy
 Properties of Matter

Intensive Properties Extensive Properties

• Temperature • Mass
• Pressure • Amount in Moles
• Density = Mass ÷ Volume • Volume
• Molar Volume= Volume ÷ Moles • Area

The ratio of two extensive

properties gives an
intensive property.
 State Variables

• Pressure (P)
• Volume (V)
System • Temperature (T)
𝑃, 𝑉, 𝑇, 𝑛, 𝑥𝑖 • Amount in moles (n)
• Composition (x1, x2, …)
State Variables
 Conversion of Units

Ex: Convert 1,000 mmHg to atm.

Cancellation
of units
𝟏 𝒂𝒕𝒎
𝟏𝟎𝟎𝟎 𝒎𝒎𝑯𝒈 × = 𝟏. 𝟑𝟐 𝒂𝒕𝒎
𝟕𝟔𝟎 𝒎𝒎𝑯𝒈
Given unit Conversion Desired unit
factor
 Conversion of Units

Ex: What is the mass of 6 moles H2O in kg?

𝟏𝟖 𝒈 𝟏 𝒌𝒈
𝟔 𝒎𝒐𝒍 × × = 𝟎. 𝟏𝟎𝟖 𝒌𝒈
𝒎𝒐𝒍 𝟏𝟎𝟎𝟎 𝒈

Follow-up: Convert 5 mg of glucose to moles.

 Conversion of Units

Ex: Convert 86.7oC to kelvins.

𝟖𝟔. 𝟕 + 𝟐𝟕𝟑. 𝟏𝟓 = 𝟑𝟓𝟗. 𝟖𝟓 𝑲

Follow-up: What is the normal body temperature in kelvin?

Zeroth Law of Thermodynamics

System A System B

TA = 200 K TB = 400 K

System A System B
Thermal
Equilibrium:
TA = ? TB = ? TA = TB
 Zeroth Law of Thermodynamics

System A System C System B

TA = 200 K TC = 350 K TB = 400 K

System A System C System B

TA = ? TC = ? TB = ?
 Zeroth Law of Thermodynamics

At thermal equilibrium, TA = TC = TB

System A System C System B

TA = ? TC = ? TB = ?
TA = TC TB = TC

Zeroth Law: If two objects A and B are in thermal equilibrium with a third
object C, then all three objects are in thermal equilibrium with each other.
 Equations of State for Pure Gases

General EOS
𝑃 = 𝑓(𝑛, 𝑉, 𝑇)
System
𝑃, 𝑉, 𝑇, 𝑛 Ideal Gas
𝑃𝑉 = 𝑛𝑅𝑇

Real Gas
More complex equations
 The Ideal Gas Law: An Experimental Result

Boyle’s Law Avogadro’s Law

𝑃1 𝑉1 = 𝑃2 𝑉2 𝑉1 𝑉2
.

(at constant n, T)
=
𝑛1 𝑛2
Ideal Gas Law
.

(at constant T, P)

𝑃𝑉 = 𝑛𝑅𝑇
Charles’ Law Gay-Lussac’s Law
𝑉1 𝑉2 𝑃1 𝑃2
= =
𝑇1 𝑇2 .
𝑇1 𝑇2 .

(at constant n, P) (at constant n, V)

 The Universal Gas Constant, R
(volume unit) x (pressure unit)
Ideal Gas Law Units of R :
(moles) x (temperature unit)
𝑃𝑉 = 𝑛𝑅𝑇 (unit of energy)
or (moles) x (temperature unit)
 Solving Problems using the Ideal Gas Law
Ex: A gas that evolved during the fermentation of glucose has a volume
of 0.78 L when measured at 20.1°C and 1.0 atm. What was the volume
of this gas at the fermentation temperature of 36.5°C? Assume ideal
gas behavior.

Answer: 0.82 L

Follow-up: How many moles of gas was produced?

 Solving Problems using the Ideal Gas Law
Ex: Air entering the lungs ends up in tiny sacs called alveoli from
which oxygen diffuses into the blood. The average radius of the alveoli
is 50 μm. Assuming that the pressure in the alveoli is 1.0 atm and the
temperature is 37°C, calculate the number of moles of air in one
alveolus.

Answer: 2.0 x 10-11 mol

 Ideal Gas Law: Applications
Molar Mass Determination and Density
Molar Mass:
𝑚𝑅𝑇 𝜌𝑅𝑇
𝑚 𝑀= =
𝑀= 𝑃𝑉 𝑃
Ideal Gas Law 𝑛
How does gas density vary
𝑃𝑉 = 𝑛𝑅𝑇 Density: with the following
parameters?
𝑃𝑀 • Molar mass
𝜌= • Pressure
𝑅𝑇 • Temperature
 Ideal Gas Law: Applications
Ex: The density of air at 1 atm and 25oC is 1.159 g/L. Assuming that air
behaves as an ideal gas, calculate the molar mass of air.

Answer: 28.36 g/mol

 Ideal Gas Law: Applications
Chemical Reaction Stoichiometry
Stoichiometric
𝑃𝑉 = 𝑛𝑅𝑇 Ratio
Amount of Amount of other
Gas Data
gas in moles reactant/product in
(P, V, T)
(n) moles (n)
Molar Molar
Mass Mass

Mass of the other

Mass of gas
reactant/product
(m)
(m)
 Ideal Gas Law: Applications
Ex: The metabolic oxidation of glucose, C6H12O6, in our bodies produces
CO2, which is expelled from our lungs as a gas:

𝐶6 𝐻12 𝑂6 𝑎𝑞 + 6𝑂2 𝑔 → 6𝐶𝑂2 𝑔 + 6𝐻2 𝑂(𝑙)

Calculate the volume of dry CO2 produced at body temperature (37°C)

and 0.970 atm when 24.5 g of glucose is consumed in this reaction.

Answer: 21.4 L

Follow-up: Calculate the volume of oxygen you would need, at 1.00 atm
and 298 K, to completely oxidize 50.0 g of glucose.
 Gas Mixtures and Partial Pressure
At constant V and T,

He N2 O2 Mixture

Dalton’s Law: The total pressure exerted by a gas mixture is the sum of
the partial pressures of its components.
 Gas Mixtures and Partial Pressure
At constant V and T,
Dalton’s Law
𝑃𝑇 = ෍ 𝑃𝑖 = 𝑃1 + 𝑃2 + 𝑃3 + ⋯
𝑛 𝑇 𝑅𝑇 𝑛1 𝑅𝑇 𝑛2 𝑅𝑇 𝑛3 𝑅𝑇 𝑃𝑇 = ෍ 𝑃𝑖
= + + +⋯
𝑉 𝑉 𝑉 𝑉
𝑛1 𝑃1 𝑛2 𝑃2
Mole fraction 𝑥1 = 𝑛 = 𝑃 𝑥2 = =
𝑛 𝑇 𝑃𝑇
𝑇 𝑇
of each
component: 𝑥3 =
𝑛3 𝑃3
= 𝒙𝒊 =
𝒏𝒊
=
𝑷𝒊 Partial Pressure
𝑛 𝑇 𝑃𝑇 𝒏𝑻 𝑷𝑻
𝑃𝑖 = 𝑥𝑖 𝑃𝑇
What is the sum of all the mole fractions, σ 𝑥𝑖 =?
 Gas Mixtures and Partial Pressure

Ex: Air is roughly 79% nitrogen and 21% oxygen (by volume or mole percent).
The human body functions best at normal atmospheric pressure of 1 atm.
a. What is the corresponding optimal partial pressure of oxygen?
b. In deep-sea diving, the total pressure can go as high as 4 atm. To maintain
the optimal partial pressure of oxygen, by how much should the oxygen
content in the air supply of divers be reduced?

Answer: (a) 0.21 atm, (b) Reduced to 5.3%

Follow-up: A condition called nitrogen narcosis can occur when the partial
pressure of nitrogen exceeds 1 atm. What is the maximum allowable nitrogen
content of air for divers at 4 atm pressure?
Real Gases: Deviation from Ideal Behavior

Molar
Volume:

𝑉ത =
𝑉
Compressibility
Ideal Gas 𝑛
Factor:
Law 𝑃𝑉ത
𝑃𝑉 = 𝑛𝑅𝑇 𝑍=
𝑅𝑇

What is the value of 𝑍 for an ideal gas?

Real Gases: Deviation from Ideal Behavior

lim 𝑍 = 1
𝑃→0

Z vs P plot for various gases at 273 K

Real Gases: Deviation from Ideal Behavior

Attractive
Easier to
𝑍 < 1 forces
Compress
dominate

Negligible
𝑍 = 1 Ideal Gas
IMF

Repulsive
Harder to
𝑍 > 1 forces
Compress
dominate
 Real Gases: Deviation from Ideal Behavior

van der Waals EOS:

𝑛𝑅𝑇 𝑛2 𝑎
𝑃= − 2
𝑉 − 𝑛𝑏 𝑉
Correction for Correction for
molecular intermolecular
volume forces

How is the van der Waals EOS expressed

in terms of molar volume (𝑉)?
ത
 Real Gases: Deviation from Ideal Behavior

van der Waals EOS: Redlich-Kwong EOS:

𝑅𝑇 𝑎 𝑅𝑇 𝐴
𝑃= − 2 𝑃= −
𝑉ത − 𝑏 𝑉ത 𝑉ത − 𝐵 ത 𝑉ത + 𝐵)
𝑇(𝑉)(

What are the units of the Redlich-Kwong

constants, 𝐴 and 𝐵?
 Real Gases: Deviation from Ideal Behavior
Ex: The molar volume of ethane (C2H6) gas at 350 K is 0.1379 L mol-1.
Estimate the pressure of the gas using:
(a) The ideal gas equation
(b) The van der Waals EOS
a = 5.47 atm L2 mol-2, b = 0.0651 L mol-1
(c) The Redlich-Kwong EOS
A = 96.89 atm L2 mol-2 K-0.5, B = 0.04515 L mol-1

Answer: (a) 208.3 atm, (b) 106.9 atm, (c) 104.5 atm

The experimentally-measured pressure of ethane at 350 K is 98.69 atm. Which

EOS gave the closest value?
 Real Gases: Deviation from Ideal Behavior

Virial EOS:
𝐵 𝐶 𝐷 ′ ′ 2 3
𝑍 = 1 + + 2 + 3 + ⋯ = 1 + 𝐵 𝑃 + 𝐶 𝑃 + 𝐷𝑃 + ⋯
𝑉ത 𝑉ത 𝑉ത
In general, 𝐵 >> 𝐶 >> 𝐷 …
B = 2nd virial coefficient
C = 3rd virial coefficient The virial EOS is more general and
… and so on accurate (if the coefficients are
(temperature-dependent) known), but tells us nothing about
molecular behavior.
 Real Gases: Deviation from Ideal Behavior
Ideal Gas
Z vs P plot for N2 at different T
At what conditions (P, T) does a gas
approach ideal gas behavior?
• High/Low Pressure
Pressure?
• High/Low Temperature
Temperature?
At low temperatures:
• Z vs P exhibits a minimum (Z < 1)
At high temperatures:
• Z indefinitely increases with P
• The slope approaches zero (Z = 1)
 Math Intervention: Partial Derivatives
Multivariable function: 𝑧 = 𝑓(𝑥, 𝑦, … )

𝜕𝑧 The multivariable
Partial Derivative: function
𝜕𝑥 𝑦
The variable being The variable treated as
differentiated constant

Example: 𝑧 = 𝑥 2 𝑦 + 𝑥𝑦 2
𝜕𝑧 2
𝜕𝑧
= (2𝑥)𝑦 + 𝑦 = 𝑥 2 + 𝑥(2𝑦)
𝜕𝑥 𝑦
𝜕𝑦 𝑥
 Real Gases: Deviation from Ideal Behavior
Boyle Temperature (TB)
The temperature where the following conditions are met:
• The 2nd virial coefficient, 𝐵 = 0
• The slope of Z vs P is horizontal near zero:
𝜕𝑍
lim =0
𝑃→0 𝜕𝑃
𝑇
𝑎
For a van der Waals gas, 𝑇𝐵 =
𝑏𝑅
At TB, the relative minimum of Z vs P disappears, and
the gas behaves most ideally at a wider range of low
pressures than any other temperature.
 Condensation and the Critical State

Critical Point Boyle’s Law • Hyperbolic curve

• Obeyed at high T > TC
(TC, PC)
𝑃𝑉 = 𝑘
Liquid .

Decreasing
Temperature At lower temperatures (T < TC),
• Isotherm crosses the two-phase
region: liquefaction can occur
Two-Phase = TC • Critical Point (TC)
Region Vapor ➢ temperature above which no
condensation can occur
➢ Zero slope & inflection point
𝜕𝑃 𝜕2𝑃
Isotherms of CO2: =0 2
=0
𝜕𝑉 𝑇 𝜕 𝑉 𝑇
constant-temperature curves
 Condensation and the Critical State
Liquefaction of CO2 (compression at constant temperature, T < TC)
Supercooled Almost vertical slope:
Liquids are nearly
Liquid incompressible

Horizontal: The
phase change occurs
at constant pressure

Superheated
Vapor
Two-Phase
Region
Point (a) Point (b) Point (c)
Saturated Vapor Liquid-Vapor Equilibrium Saturated Liquid
- onset of - liquid and vapor - onset of
condensation phases coexist evaporation
 The Kinetic Molecular Theory of Gases
Chaotic Motion: Gases are composed of discrete molecules in
1 ceaseless, random motion.

Negligible Volume: The volume of gas particles is negligible

2 compared to the volume of the container.

No IMFAs: Gas molecules do not exert forces with one

3 another, except during collisions.

Elastic Collisions: When molecules collide among themselves

𝟑
4 and the container, energy and momentum are conserved.
𝑲𝑬 = 𝑹𝑻
𝟐
Temperature: The average kinetic energy of the molecules is
5 directly proportional to the absolute temperature.
 The Kinetic Molecular Theory of Gases
Maxwell-Boltzmann Distribution Law: Most probable speed: the speed
exhibited by the largest number of
molecules
NOTE:
𝒖𝒎𝒑 ഥ
𝒖 𝒖𝒓𝒎𝒔 𝑢𝑚𝑝 < 𝑢ത < 𝑢𝑟𝑚𝑠 2𝑅𝑇
𝑢𝑚𝑝 =
𝑀
Relative
Probability, 𝑀
3/2
−
𝑀𝑢2
𝑢2 𝑒 2𝑅𝑇
Average speed: Mean speed of all
f(u)
𝑓 𝑢 = 4𝜋
2𝜋𝑅𝑇
molecules
[a.k.a.
Fraction of 8𝑅𝑇
𝑢ത =
molecules 𝜋𝑀
moving at
speed u] Root-mean-square speed: Speed
of a molecule whose KE is equal to
the average KE of all molecules
Speed, m/s 3𝑅𝑇
𝑢𝑟𝑚𝑠 =
Speed Distribution of Argon at 500 K 𝑀
 The Kinetic Molecular Theory of Gases
Speed Distribution of N2 at different temperatures Speed Distribution of selected gases at 300 K

𝑓(𝑢) 𝑓(𝑢)

𝑢, 𝑚/𝑠 𝑢, 𝑚/𝑠

Effect of T Effect of M
For the same gas, there is a greater At a given temperature, lighter
fraction of molecules with higher speeds molecules are moving faster on average
at higher temperatures. compared to heavier molecules.
The Kinetic Molecular Theory of Gases

Interpreting Temperature
The higher the temperature of a gas, the
faster the average speed of its molecules.
1
𝑇 ∝ 𝐾𝐸 = 𝑚𝑢2
2

Origin of Pressure
Pressure arises due to frequent collisions
of gas particles with the container.
𝐹
𝑃=
𝐴
 The Kinetic Molecular Theory of Gases

Gay-Lussac’s Law Boyle’s Law Avogadro’s Law

If temperature increases, the As the gas is compressed, Adding more molecules at
molecules move faster, creating molecule-wall collisions become constant pressure pushes the
more frequent collisions more frequent container outward
high 𝑇-> high 𝑃 low 𝑉 -> high 𝑃 high 𝑛 -> high 𝑉
 Diffusion and Effusion: Graham’s Law

Diffusion Effusion
Movement of a gas Passage of a gas
from higher to lower through a pinhole or
concentration orifice

Rate of Effusion is Graham’s Law of Effusion

directly proportional to: Rate of Effusion is
▪ molecular speeds inversely proportional 𝑟𝑎𝑡𝑒1 𝑀2
▪ amount of gas to: =
effused ▪ Effusion time 𝑟𝑎𝑡𝑒2 𝑀1
▪ distance traveled