Chemistry: for

Engineering Students

Chapter 5: Gases
5.1 INSIGHT INTO Air Pollution
5.2 Pressure
5.3 History and Application of the Gas Law
5.4 Partial Pressure
5.5 Stoichiometry of Reactions Involving Gases
5.6 Kinetic–Molecular Theory and Ideal Versus Real Gases

Feb-16 Chapter-5 1
Chemistry: for
Engineering Students Air pollution
Clean Air is a gaseous mixture of compounds and elements.

Dry (clean) air composition

Component mol %
N2 78.085
~99%
O2 20.946
Ar 0.934
CO2 0.0314
Ne 0.00182
He 0.000524
Trace components
CH4 0.00015
from natural sources
Kr 0.000114
H2 0.000058
NO 0.000031
Xe 0.00000087
Feb-16 Chapter-5 2
Chemistry: for
Engineering Students Air pollution
Air pollution: is one of the unintended but unavoidable side effects of modern society.
The issues surrounding the monitoring, prevention, and remediation of air pollution
involve an exceedingly complex interplay between science, business, and public policy.

Air pollutants that pose specific risks for human health are trace components
emitted by anthropogenic sources (e.g. industry, transportation vehicles, etc.)

Photochemical
• NO2 reactions
• VOC Secondary
Primary O3
• SO2, Pollutants
Pollutants
• Soot particles
Etc.

SMOG

Feb-16 Chapter-5 3
Chemistry: for
Engineering Students Air pollution
Concentration ranges (ppm) of primary pollutants

Pollutant Main Heavily Urban Clean

Source Polluted Area Area Air

Sulfur dioxide SO2 1-2 0.08 < 0.01

Nitrogen oxides NOx 0.2 0.05 < 0.01

Carbon monoxide CO 10-50 10 < 0.05

Volatile Organic CxHy >3 3 0

Chemicals
Pb, Particulate Pb(Et)4
matter Soot,
etc.

Concentration 10 mol CO 10 CO molecules

in ppm Ex.: 10 ppm CO = 6 = 6
10 mol air 10 air molecules
Parts per million
Feb-16 Chapter-5 4
Chemistry: for
Engineering Students Air pollution
Some characteristic properties of Gases
(regardless of their chemical composition)

Gas Liquid Solid

Expands to fill its Adopts the shape of a portion of Keeps own shape and
container, but does not expand volume
container
to fill its container
∆V Compressible Virtually
∆P incompressible
Changes volume Volume remains nearly constant
∆V dramatically with with changing T

∆T changing T
Diffusion within Diffusion within a liquid occurs Diffusion within a solid
slowly occurs extremely slowly
a gas occurs
(generally, it is negligible)
rapidly
Flows readily Flows readily Does not flow

Feb-16 Chapter-5 5
Chemistry: for
Engineering Students Air pollution
Some characteristic properties of Gases

Example: H2O 0C at 1 atm

m g
Very weak interaction
Low ρ= ≈ 10−3
density V mL

Average speed ~105 cm/s Average intermolecular

separation> 10 Å

High value of Nearly zero

kinetic potential
energy energy

U kin >> 0 U pot ≈ 0

Container Water vapor
Feb-16 Chapter-5 6
Chemistry: for
Engineering Students Pressure

Pressure (P) and temperature (T) are essential physical

quantities for characterizing the macroscopic state of matter….
….avoiding thus the individual molecular description.

Pressure (P) is derived from other (fundamental) physical quantities.

SI Unit N
Pressure: is defined as the (Pascal)
Pa = 2
applied force per unit of area m
Other P units
F⊥
F⊥ 105 Pa 101325 Pa
Pressure P= 1bar 1 atm
A A 760 mm Hg
1 atm
Feb-16 Chapter-5 7
Chemistry: for
Engineering Students Pressure
Pressure exerted by a gas

The gas is an ensemble of

~NA molecules moving
rapidly and chaotically!
Momentum
change
The atoms or molecules of an ideal gas do
not interact with one another, and the atoms
or molecules can be treated as point masses. Elastic collision

The pressure exerted by a gas on the

container confining the gas arises from
collisions of randomly moving gas molecules
with the container walls.
2
nN A m v nRT
P= =
Feb-16
V 3 V Chapter-5 8
Chemistry: for
Engineering Students Pressure

Hg manometer
Pressure exerted by a gas can be
measured by means of a manometer.
(Pressure gauge)

The height difference in mmHg gives

the pressure difference between the
gas in the vessel and open
atmosphere.

Example:
Measuring
tire Hg(l)
pressure
Bourdon
Gas pressure
9
Chemistry: for
Engineering Students Pressure
Modern pressure gauges can measure exceedingly
small pressure (10-14 mm Hg) or changes in pressure

P down to 0.001 torr

P down
to 10-11 torr

Capacitance manometer: As the gas
molecules strike the diaphragm, the force of
the collisions determines the space between
the diaphragm and the fixed electrode
assemblies.
Feb-16
Ionization Gauge: Electrons emitted from the hot
filament collide with gas molecules and knock an
electron free. The resulting cations are collected at
the center of the gauge, and the current they
produce is a measure of the gas pressure.
Chapter-5 10
Chemistry: for
Engineering Students History and Application of the Gas Laws
In many ways gases are the most easily understood form of matter
because they exhibit very similar physical properties.
Molecular model of
ideal gas Experimental
Boyle’s bounds
•Intermolecular
interactions are law of ideal gases
1
negligible. V∝ •Low or moderate
P pressure (P < 10
•Molecules are V n atm).
point-like particles. P T
Avogadro’s
•High Temperature
•Molecules move ( T > 0oC).
rapidly and randomly Ideal gas V ∝n
•Small molar mass
•The total kinetic (M< 50 g/mol)
energy is conserved Charles’s
law
Feb-16 Chapter-5
V ∝T 11
Chemistry: for
Engineering Students History and Application of the Gas Laws
The three laws of ideal gases are
Ideal Gas Laws merged into a single equation: The
ideal gas equation. The required R
Boyle’s constant can be expressed in various
1
V∝ ( constant T and n )
units.
P
Charles’ nT nT
V ∝T ( constant P and n ) V∝ V =R
P P
Avogadro’s
( constant P and T ) (T expressed in K) Ideal Gas
V ∝n constant

atm L
R = 0.08206
Ideal Gas Equation K mol

Pa m3 J
PV = nRT R = 8.3145 ≡
K mol K mol
Feb-16 Chapter-5 12
Chemistry: for
Engineering Students History and Application of the Gas Laws
Applications of the ideal gas

A hair spray bottle has an internal pressure of 3.8 atm at 23 oC. In case of
fire, temperature can reach 400 oC. Would the aluminum bottle explode if
the aluminum sheet cannot hold pressures that exceed 8.0 atm?

Strategy: Apply the ideal

Sketch of the process at work gas equation to the
T2 = 400 o C initial and final states
P1 = 3.8 atm T1 = 23 o C P2 ?
V n V n
Hair conditioner(g) Hair conditioner(g) PV = nRT1  P1 T1
 =
1
P and T
state 1 increase state 2
PV
2 = nRT2  P2 T2
at constant V

 T2   400 + 273.15  Bottle will

P2 =   P1 =  ·3.80 atm = 8.6 atm > 8 atm
T
 1  23 + 273.15  explode!
Feb-16 Chapter-5 13
Chemistry: for
Engineering Students History and Application of the Gas Laws
Applications of the ideal gas
• Many gases are shipped in high-pressure containers. Consider a
steel tank whose volume is 210 L that contains O2 gas at a pressure
of 16.500 kPa at 23 oC .
(a)What mass of O2 does the tank contain?
(b) What volume would the gas occupy at STP?
(c) At what temperature would the pressure in the tank equal 150.0
atm?
(d) What would be the pressure of the gas, in kPa, if it were
transferred to a container at whose volume is 55.0 L?

Feb-16 Chapter-5 14
Chemistry: for
Engineering Students History and Application of the Gas Laws

• A vessel contains 1.15 g H2O(l) in equilibrium with water vapor at 30.°C.

At this temperature, the vapor pressure of H2O(l) is 31.82 torr. What
volume increase is necessary for all the water to evaporate?

Feb-16 Chapter-5 15
Chemistry: for
Engineering Students Partial Pressure
PV=nRT is valid either for pure substances (individual gases
like N2(g), He(g), …) or mixtures (e.g., air).

The pressure of a mixture of gases is the sum of the

partial pressures of the component gases.

Gaseous mixture (A, B,…)

PV = nRT = ( nA + nB + ...) RT = nA RT + nB RT + ... =

= PAV + PBV + ... = ( PA + PB + ...) V

Partial pressures account for the composition (concentration) of the

gaseous mixture
Dalton’s law of P = PA + PB + ...
Partial Pressures

Feb-16 Chapter-5 16
Chemistry: for
Engineering Students Partial Pressure

Relation between composition and partial pressures

XA is adimensional
nA
Molar XA = 0 < XA <1
fraction n N

∑X
i =1
i =1
Total number
of moles Another form
of stating Dalton’s law
Ratio of pressures nA RT
transforms
PA
=
nRT
V =
nA
= XA PA = P· X A
into molar fractions P n
V

Feb-16 Chapter-5 17
Chemistry: for
Engineering Students History and Application of the Gas Laws
• Calculate the average molar mass of dry air if it has a density of 1.17 g/L at
21.0 oC and 740.0 torr. 2) Assuming that dry air is binary mixture of oxygen
and nitrogen, find out the partial pressure of each component.

1) Strategy: Rewrite the ideal gas equation in terms of the gas density ρ, P
and T. mass / molar mass
n P mM P m PM
PV = nRT ⇒ = ⇒ = ⇒ ρ= =
V RT V RT V RT
Solution: atm L
0.08206 ( 273.15 + 21) K
RT g K mol g
M air = ρ air = 1.17 = 29.0
P L ( 740.0 760 ) atm mol
2) Strategy: Mair is the average of MN2 and MO2 weighed by their abundances
(the molar fractions x). Use also the Dalton’s law.
X N 2 M N 2 + X O2 M O2 = M air 
 M air − M O2 29.0 − 32.00
X N 2 + X O2 = 1  PN 2 = P = 740.0 torr = 5.6·102 torr
 M N 2 − M O2 28.02 − 32.00
PN2 = P X N 2 , PO2 = P X O2 
PO2 = P − PN 2 = 7.400·102 − 5.6·102 = 1.8·102 torr
Feb-16 Chapter-5 18
Chemistry: for
Engineering Students Partial Pressure
• A piece of dry ice (solid carbon dioxide) with a mass of 5.50 g is placed
in a 10.0-L vessel that already contains air at 705 torr and 24 oC. After
the carbon dioxide has totally vaporized, what is the partial pressure of
carbon dioxide and the total pressure in the container at 24 oC?

Feb-16 Chapter-5 19
Chemistry: for
Engineering Students Partial Pressure
• A sample of 5.00 mL of diethylether (ρ=0.7134 g/mL) is introduced into a
6.00-L vessel that already contains a mixture of N2 and O2, whose partial
pressures are 0.751 atm and 0.208 atm, respectively. The temperature is
held at 35.0 oC , and the diethylether totally evaporates.
(a)Calculate the partial pressure of the ethylether.
(b)Calculate the total pressure in the container.

Feb-16 Chapter-5 20
Chemistry: for
Engineering Students Stoichiometry of Reactions Involving Gases
• When gases are involved in a chemical reaction, the ideal gas law often
provides the best way to determine n.
• Using the ideal gas law in a stoichiometry problem does not involve any
new ideas. It just combines two kinds of calculations (PV=nRT and
stoichiometric calculations involving molar ratios)

Volume of A (L) Volume of B (L)

VA + VB ?
Ideal gas Ideal gas
eq. A Gas
eq. B
PA syringes
nA = VA nB =
PA
VB
RT RT

Moles of A (mol) Moles of B (mol)

“A(g) + B(g) +…→ P(g) + Q(g) + …”
Feb-16 Chapter-5 21
Chemistry: for
Engineering Students Stoichiometry of Reactions Involving Gases
Avogadro’s Law
Under the same conditions of P and T, a given V of an ideal gas contains the
same number of molecules regardless of the identity of the gas.

Standard Pressure and Temperature (SPT)

of ideal gas= 1.0 atm and 0 oC

One mole of ideal gas occupies 22.4 L at SPT conditions.

• Which V of O2(g) is necessary to completely react with 2.54 L of NH3
measured at the same conditions?
• 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2(g)

Feb-16 Chapter-5 22
Chemistry: for
Engineering Students Stoichiometry of Reactions Involving Gases
• An experiment often run in general chemistry laboratories involves determining the
number of moles of gas generated in a reaction. Sometimes the gas is collected over
water. Zn(s) reacts with strong acids as HCl(aq) to give H2(g). Calculate the volume
occupied by the wet H2(g) if 25.00 g Zn(s) react in excess of HCl(aq).

Data: T = 20 ºC Patmospheric = 805 mmHg. Pvap0= 17.45 mmHg for H2O at 20 oC.

HCl(aq)

H2 (g) + H2O(g)

Zn(s)
water
Chemistry: for
Engineering Students
Kinetic-Molecular Theory and Ideal vs Real Gases
Non-ideal behavior is frequently seen in gases at very high pressures
(e.g., gas in the cylinder of an engine or in an industrial processing plant). The atomic
description of gases in terms of the kinetic-molecular theory is crucial for
understanding real gases.

1. A gas is made up of a vast number of particles, and these

particles are in constant random motion.
2. Particles in a gas are infinitely small; they occupy no volume.
3. Particles in a gas move in straight lines except when they collide
Elements with other molecules or with the walls of the container. Collisions
of the with each other and with the walls of the container are elastic, so
that the total kinetic energy of the particles is conserved (at
Kinetic equilibrium) .
Theory
4. Particles in a gas interact with each other only when collisions
occur.
5. The average kinetic energy of the particles in a gas
is proportional to the absolute temperature and does
not depend on the identity of the gas. 1 3
U kin = M v 2 = RT
Feb-16 Chapter-5 2 24 2
Chemistry: for
Engineering Students
Kinetic-Molecular Theory and Ideal vs Real Gases
Distributions of molecular
speeds for CO2 molecules at
three different temperatures.

The distribution function

that describes the
speeds of a collection of
gas particles is known
as the Maxwell-
Boltzmann distribution
3
Distributions of molecular
N (v)
2
Mv
 M  2 − 2 RT
2 speeds for four different
= 4π   ve
N total  2π RT  gases at the same
temperature

Feb-16 Chapter-5 25
Chemistry: for
Engineering Students
Kinetic-Molecular Theory and Ideal vs Real Gases

How to discriminate the regime of ideal gas

behavior from that of real gas?
ideal gas regime ↔ P < 1-10 atm and T > 273 K and M < 50 g/mol;
Large speed and long mean free path~70Å

Intermolecular interactions can be safely ignored. They are negligible …

Real (non-ideal) gas regime ↔ P > 1-10 atm or T < 273 K or M > 50 g/mol;
Low speed and/or short mean free path~1-5Å

P↑
…then intermolecular interactions DO count
and influence gas properties. Condensation of
real gases into liquids can be achieved either T↓
by gas compression and/or gas cooling.
Chemistry: for
Engineering Students
Kinetic-Molecular Theory and Ideal vs Real Gases
• Analyze the Figure shown below and discuss the effect of pressure and
molar mass on the behavior of several real gases. Data for 1 mol of gas in all
cases. Data for N2, CH4, and H2 are at 300 K; for CO2 data are at 313 K because
under high pressure CO2 liquefies at 300 K.

PV 1 mol
Z=
RT

Z ideal = 1

Feb-16 Chapter-5 27
Chemistry: for
Engineering Students
Kinetic-Molecular Theory and Ideal vs Real Gases
Correcting the Ideal Gas Equation for Real Gases

The ideal gas equation PV = nRT is inexact. We need other state

equations containing parameters related to intermolecular forces and
the actual size of the gas molecules.

van der Waals Equation

 n2 a 
 P + 2  (V − nb ) = nRT
 V 

Other relationships that are satisfied

by ideal gases, such as Dalton's law,
are equally inaccurate.
Chemistry: for
Engineering Students
Kinetic-Molecular Theory and Ideal vs Real Gases
• You want to store 165 g of CO2 gas in a 12.5 L tank at room temperature
(25°C). Calculate the pressure the gas would have using (a) the ideal
gas law and (b) the van der Waals equation. (For CO2, a = 3.59 atm
L2/mol2 and b = 0.0427 L/mol.)

Feb-16 Chapter-5 29
Chemistry: for
Engineering Students
Kinetic-Molecular Theory and Ideal vs Real Gases
• Using the vdW equation, calculate the molar volume of CO2 at 1.0 bar
and 298 K and 50 bar and 600 K. (For CO2, a = 3.59 atm L2/mol2 and b =
0.0427 L/mol.) Hint: This problem admits only a numerical solution that can be
obtained with the help of MATLAB/Octave.

Solution
f(v0)=0

v0

Feb-16 Chapter-5 30
Chemistry: for
Engineering Students
Problems and Exercises

5.2 When ozone levels in urban areas reach unhealthy levels, residents are
typically urged to avoid refueling their cars during daylight hours. Explain how this
might help to reduce smog formation.

5.9 How do gases exert atmospheric pressure? How can atmospheric pressure be
measured?
5.10 Why do mountain climbers need to wear breathing apparatus at the tops of
high mountains such as Everest?

5.22 Why should temperature always be converted to kelvins when working with
gases in problem solving?

5.23 What evidence gave rise to the establishment of the absolute temperature
scale?

5.28 A bicycle tire is inflated to a pressure of 3.74 atm at 15°C. If the tire is heated
to 35°C, what is the pressure in the tire? Assume the tire volume doesn’t change.

Feb-16 Chapter-5 31
Chemistry: for
Engineering Students
Problems and Exercises
5.48 An experiment is being carried out to test the removal of sulfur dioxide from
gases being released by a power plant. The initial sample, which contains only
carbon dioxide and sulfur dioxide, occupies a volume of 35.0 L at a temperature of
41°C and a pressure of 715 torr. After all of the SO2 has been removed, the sample
occupies a volume of 23.5 L at a temperature of 29°C and a pressure of 715 torr.
Determine the partial pressures of both CO2 and SO2 in the initial sample.

5.52 Hydrogen gas is generated when acids come into contact with certain metals.
When excess hydrochloric acid reacts with 2.5 g of Zn (the metal product is Zn2+),
what volume of hydrogen gas is collected at a pressure of 0.93 atm and a
temperature of 22°C?
5.54 The first step in processing zinc metal from its ore, ZnS, is to react it with O2
according to the reaction,
ZnS(s) + O2(g) → ZnO(s) + SO2(g) unbalanced
If 620 kg of ZnS is to be reacted, what volume of oxygen at 0.977 atm and 34.0 °C
is needed (at a minimum) to carry out this reaction?
5.58 One way to generate oxygen is to heat potassium chlorate, KClO3 (the other
product is potassium chloride). If 386 mL of oxygen at 41°C and 97.8 kPa is
generated by this reaction, what is the minimum mass of KClO3 used?

Feb-16 Chapter-5 32
Chemistry: for
Engineering Students
Problems and Exercises
5.64 Automakers are always investigating alternative reactions for the generation of
gas to inflate air bags, in part because the sodium produced in the decomposition of
NaN3 presents safety concerns. One system that has been considered is the
oxidation of graphite by strontium nitrate, Sr(NO3)2, as shown in the equation below:
5 C(s) + 2 Sr(NO3)2(s) → 2 SrO(s) + 2 N2(g) + 5 CO2(g)
Suppose that a system is being designed using this reaction and the goal is to
generate enough gas to inflate a bag to 61 L and 1.3 atm at 23°C. What is the
minimum mass of graphite that should be used in the design of this system?

5.72 Use kinetic theory to explain what happens to the pressure exerted by a gas
as its temperature is increased.
5.73 The adjacent figure shows the distribution of
speeds for two samples of N2 gas. One sample
is at 300 K, and the other is at 1000 K.
Which is which?

5.85 A gas mixture contains 10.0% CH4 and 90.0% Ar by moles. Find the density of
this gas at 250.0°C and 2.50 atm.

Feb-16 Chapter-5 33
Chemistry: for
Engineering Students
Problems and Exercises
5.88 You work in a semiconductor production plant that relies on several
chlorofluorocarbons in its manufacturing process. One day, you find an unlabeled
gas cylinder, and you are assigned to figure out what is in the tank. First you fill
a 1.000 L flask with the gas. At a pressure of 250.0 torr and a temperature of
25.00°C, you determine that the mass of the gas in the flask is 2.2980 g. Then you
send the flask to an outside lab for elemental analysis, and they report that
the gas contains 14.05% C, 44.46% F, and 41.48% Cl by mass. Find the molecular
formula of this gas.
5.90 A mixture of Ar (0.40 mol), O2 (0.50 mol), and CH4 (0.30 mol) exerts a pressure
of 740 mm Hg. If the methane and oxygen are ignited and complete combustion
occurs, what is the final pressure of Ar, CO2, H2O, and the remainder of the excess
reactant? What is the total pressure of the system?
10.62 (TCS) Acetylene gas can be prepared by the reaction of calcium carbide
(CaC2) with water. The second product of the reaction is calcium hydroxide.
Calculate the volume of acetylene that is collected over water at 23 oC by reaction
of 1.524 g of CaC2 if the total pressure of the gas is 753 torr.
Hint: You need to search for the vapor pressure of water at 23 oC.
10.94 (TCS) The planet Jupiter has a surface temperature of 140 K and a mass 318
times that of Earth. Mercury (the planet) has a surface temperature between 600 K
and 700 K and a mass 0.05 times that of Earth. On which planet is the atmosphere
more likely to obey the ideal-gas law? Explain.
Feb-16 Chapter-5 34
Chemistry: for
Engineering Students

10.6(TCS) The apparatus shown here has two gas-filled

containers and one empty container, all attached to a
hollow horizontal tube. When the valves are opened and
the gases are allowed to mix at constant temperature,
what is the distribution of atoms in each container?
Assume that the containers are of equal volume and
ignore the volume of the connecting tube. Which gas
has the greater partial pressure after the valves are

Fraction of molecules
opened? A
Exam (March-2015) Assume that an exhaled breath
B
of air consists of 74.8% N2, 15.3% O2, 3.7% CO2 and
6.2% water vapor. The pressure and volume of the
exhaled gas are 0.985 atm and 455 mL, respectively,
Molecular speed
and its temperature is 37 oC.
a) Consider the following graph. If curves A and B refer to two water and carbon
dioxide, which is which? Explain.
b) How many grams of glucose (C6H12O6) would need to be metabolized to produce
this quantity of CO2 assuming a 85% yield (The chemical reaction is the same as
that for combustion of C6H12O6)
Feb-16 Chapter-5 35