Gases

Dr. Germán Pérez

 CHEM205 - GENERAL
FALL 2020
CHEMISTRY I
Department of Chemistry & Biochemistry

Objectives

10.1 Gas Pressure Chapter Goals – Study Checklist:

10.2 Gas Laws: Experimental Basis ❑ Interconvert units of pressure
10.3 The Ideal Gas Law ❑ Understand basis of gas laws (Boyle,
10.4 Gas Laws & Chemical Reactions Charles, Avogadro, Dalton)
10.5 Gas Mixtures & Partial Pressures ❑ Describe how changing one property
10.6 Kinetic Molecular Theory of Gases of a gas (P, V, T, n) changes the others
10.7 Diffusion & Effusion ❑ Use gas laws in problem-solving
10.8 Nonideal Behaviour of Gases ❑ Apply gas laws to stoichiometric
calculations
❑ Understand kinetic-molecular theory
of gases (especially the distribution
of molecular speeds) & use it to
explain gas behaviour
❑ Recognize why real gases do not
behave as ideal gases under some
conditions

(2)
 CHEM205 - GENERAL
FALL 2020
CHEMISTRY I
Department of Chemistry & Biochemistry

Gas terminology
▪ Referring to gas-phase substances:

• “gas” = substance normally in gaseous state (phase) at

ambient temperature (T) & pressure (P)
Table 10.1: He, H2, O2, N2, F2, Cl2, CO2, C3H8, etc…

• “vapour” = gaseous form of substance that is normally a

solid or liquid at ambient T & P
water vapour (steam), gasoline vapour (gas fumes)
Particles (atoms/molecules)CHEM205 - GENERAL
in a gas are VERY FAR APART FALL 2020
Department of Chemistry & Biochemistry
CHEMISTRY I
▪ lowest density state of matter
▪ particles can be squeezed closer together: compressible
▪ particles don’t interact much with each other: simple behaviour!
Zumdahl’s Figure 5.14: (b) One mole of N2(g) at STP
(a) One mole of N2(l) = 28.13 g V = 22.4 L
V = ~ 35 mL = ~ (3.3 cm)3 d = 1.2 x 10-3 g/mL
d = 0.81 g/mL

22.4 L = 22.4 dm3

Volume of one mole of N2, = 22.4 x (10cm)3
as LIQUID vs. GAS:
V(N2(g)) / V(N2(l)) = 22.4 x 103 cm3
≈ 28cm x 28cm x 28cm
= 22.4 L / 0.035 L
= 640x greater as gas! ≈ roughly 1 cubic foot
Gas PRESSURE: whatCHEM205
is it? - GENERAL
FALL 2020
Department of Chemistry & Biochemistry
CHEMISTRY I
Force caused by gas particles
colliding with container walls
PRESSURE is defined as:
FORCE per unit AREA
• Force = mass x acceleration
= mass x (velocity change/unit time)
1 N = 1 kg x (m/s2) = definition of “Newton”
• SI unit of Pressure: “Pascals” 1 Pa = 1 N/m2
= 1 (kg·m·s-2)·m-2
= 1 kg·m-1s-2
• Typical “atmospheric pressure” = 1 atm (common in chemistry)
= 101.325 kPa (common in meterology)
= 1.01325 bar (common in meterology)
= 760 mm Hg (common in chemistry)
= 760 torr (common in chemistry)
NOTE:
• in everyday life: “psi” (pounds per square inch) where 1 atm = 14.7 psi
Measuring pressure:CHEM205 - GENERAL
barometers &
CHEMISTRY I
manometers
Department of Chemistry & Biochemistry
FALL 2020

See Kotz Fig.10.2 See Kotz p.373: A Closer Look

A barometer A manometer
• dish of Hg(l) open to atmosphere • U-tube, with Hg(l)
• evacuated tube inverted into Hg • sealed on one end
• Hg rises until PHg(gravity) = Patm • gas flask on other end

• P = height of Hg column • P = difference in height of two

ends of Hg “column” in the U-
tube
P in
mm Hg  gas inlet

vacuum gas

add P in
gas mm Hg
 CHEM205
Gas Laws: Experimental Basis…  Ideal
- GENERAL
Gas Law FALL 2020
Department of Chemistry & Biochemistry
CHEMISTRY I

Gas behaviour is described by natural “laws”

Based on general observations made in 17-18th centuries by:
• Avogadro: more particles  larger volume V=an
• Boyle: higher pressure  smaller volume V = b/P
• Charles: higher temperature  larger volume V=cT

Physically: All gases essentially behave same way! (NOT chemically)

SUMMARY: The volume (V) occupied by a sample of gas is:

directly proportional to n (#moles) & T (temperature)
inversely proportional to P (pressure)…
The IDEAL
…combine laws into one equation: PV = nRT
GAS LAW
A proportionality constant: R = “the gas constant”
= 8.314 Jmol-1K-1 = 0.08206 Latmmol-1K-1
 CHEM205
Charles’ law & the absolute - GENERAL
(Kelvin) temperature scale FALL 2020
Department of Chemistry & Biochemistry
CHEMISTRY I
If measure V vs T Details about
for various gases: Avogadro’s &
(Fig.11.5) Boyle’s law exp’ts
too in Kotz 10.2…

Gases liquefy at low T…

▪ H2 bp -253°C
 Extrapolate to ▪ O2 bp -183°C
“predict” absolute
lowest possible
temperature
= 0 Kelvin
= -273.15 °C
The Kelvin scale was
proposed by W.Thomson
(aka Lord Kelvin).

K.9th Fig.10.5
 CHEM205 - GENERAL
Gases behave ideally if their CHEMISTRY
particles don’t
I interact much
Department of Chemistry & Biochemistry
FALL 2020

In an IDEAL gas, the particles (atoms/molecules)

1) do not interact with each other  particles are very far apart
2) each have ~zero volume  most of container is truly empty
3) are in constant motion  enough KE to overcome all attractions,
whether strong (polar) or weak (nonpolar)
THUS: Any gas will behave ideally…
• at LOW pressures  low concentration of particles
• at “HIGH” temperatures  particles moving quickly
Under these conditions, gases OBEY THE IDEAL GAS LAW  PV=nRT
accurately describes physical behaviour

Standard Temperature & Pressure: “STP” = 1 atm, 0°C

= conditions where
Molar volume: 22.42 L at STP most gases behave
1 mole of any gas occupies 22.42 L at STP ideally
Why memorize? calculate easily using PV=nRT… (i.e., “high T”)
 CHEM205 - GENERAL
Can use the parent gas laws individually…
FALL 2020
…to compare same sample of gasCHEMISTRY
under different
I conditions
Department of Chemistry & Biochemistry

• Boyle’s law: P  V P1V1 = P2V2 when n & T are constant

• Charles’ law: T  V V1 = V2
when n & P are constant
T1 T2

Can use PV=nRT for the two

conditions to derive needed law
(less memorizing…).
#n of gas does not change here:
V1 = nR = V2
T1 P T2
 CHEM205 - GENERAL
Sample exam question: howI many balloons?
CHEMISTRY
Department of Chemistry & Biochemistry
FALL 2020

Imagine you are filling balloons with helium from a 30.0 L gas cylinder. The “full” cylinder
contains 125 atm of He at a temperature of 26°C, and the cylinder is “empty” when the He
pressure reaches 1.05 atm
(i.e., atmospheric P) at the same temperature. Assuming ideal behaviour:
how many balloons can be filled to a 3.00 L volume at 1.05 atm & 23°C?

Approaches: conceptually simplest one uses only PV=nRT

1.) Calculate #moles He in “full” vs. “empty” tank  available He
2.) Calculate #moles He in full balloon (note new T)
3.) Divide…

#nballoon
#mol He 
#nempty
– =
#nfull

available

Full Empty Each balloon P

P = 125 atm P = 1.05 atm = 1.05 atm
V = 30.0 L V = 30.0 L V = 3.00 L
T = 26˚C T = 26˚C T = 23˚C

ANS: 1168.6 balloons (many ways to reach this answer)

(11)
To 3SF : 1170 (= more than can actually fill…  better to report 1168…
 CHEM205 - GENERAL
Gas laws & chemical rxns: anCHEMISTRY
explosive example
I
Department of Chemistry & Biochemistry
FALL 2020

What would happen if 25.0g of nitroglycerin (C3H5N3O9, MM 227.1 g/mol) were

detonated inside an evacuated, rigid 10.0 L container at 500°C?
4 C3H5N3O9(s) → 12 CO2(g) + 6 N2(g) + 10 H2O(g) + O2(g)

(a) What would the total pressure be inside the container?

ANS: 0.1101 mol C3H5N3O9  0.7982 mol gas  5.06 atm

(b) If the hot gases were released out into the atmosphere, where the pressure is
1.00 atm, what would the total volume of gas be? Assume the temperature
remains at 500°C. ANS: 50.6 L
(c) Now consider that the original solid occupied approximately 15.0 cm3 (1cm3
= 1mL, or 1dm3 = 1L). How many times greater is the volume of the products
compared to reactants (at 1 atm P)? ANS:
much of destructive force of explosives comes 50.6 L x (10cm)3
from sudden formation of large volumes of gas 1L
forces everything out of the way… = 50600 cm3
≈ 3400 x larger!
 CHEM205 - GENERAL
Gas mixtures – Dalton’s Law of Partial Pressures
CHEMISTRY I
Department of Chemistry & Biochemistry
FALL 2020

For mixture of gases in container: PTotal = P1 + P2 + … + Pn

Each gas contributes
to the total pressure…
BUT…
the partial pressure of each gas is
SAME AS IF ALONE in container!
• P1 depends only on # moles of gas 1
Z’s Fig.5.12 (use PV=nRT)
• If know Ptotal & mole ratio of gases,
can calculate partial pressures
 CHEM205 - GENERAL
Our explosion example: nowCHEMISTRY
think aboutIpartial pressures
Department of Chemistry & Biochemistry
FALL 2020

25.0g of nitroglycerin (C3H5N3O9, MM = 227.1 g/mol) detonated

inside an evacuated rigid 10.0 L container at 500°C…
4 C3H5N3O9(s) → 12 CO2(g) + 6 N2(g) + 10 H2O(g) + O2(g)

(d) Calculate the partial pressure of oxygen in the container.

QUESTION: ANS: 0.174 atm
Do we need to know the total P ? (1/29th of PTOT)

ANS: no -- Could use stoichiometry to find #nO2 formed,

then convert to PO2 using PV=nRT
(e) Imagine this explosion occurred on a large scale in a building,
& the air in the room was displaced by the gaseous rxn products at 1 atm.
Would a person who survived the explosion be able to breathe comfortably
in that room?
(assume T = 25°C if use PV=nRT approach)
ANS: PO2 = (1/29) x 1.00 atm = 0.0345 atm
but we’re used to PO2 = 0.21 atm (21% of atmospheric P)
so we would not get enough oxygen now…
 Earth’s Atmosphere
Interesting real-world applications: (p.392 A Closer Look)

▪ Atmospheric pressure
Pressure (millibars)
1 atm = 1013 mbar

caused by weight of

Height (km)
atmosphere’s gases
▪ at sea level: Ptot ≈ 1 atm
▪ oxygen: P O2 0.21 atm

dangerously low P O2 > 8000 m

“the death zone”
Temperature (C°) cellular O2 exchange system
evolved with this P O2
 functions poorly with less!
▪ IMPLICATION: partial pressure of oxygen drops with altitude
▪ High altitude: lower Ptot (due to lower thickness of atmosphere above)
• top of Mt. Everest: Ptot = 0.29 atm of which 21% is from O2
(elevation 8848 m)  P O2 = 0.061 atm
Interesting real-world applications: Deep sea diving

▪ At surface: normal air, 21% O2  P O2 = 0.21 atm

78% N2  P N2 = 0.78 atm
▪ Using a SCUBA tank: P’s must be balanced inside & out…
i.e., pressure of air = pressure exerted on body
= 2 atm at 33 feet below water
 because O2 is still 21% of the air in the tank,
P O2 = 0.21 x 2 atm = 0.42 atm oxygen
P N2 = 0.78 x 2 atm = 1.56 atm nitrogen
▪ Problems: high P N2 (depths ~below 100ft) leads to
huge increase in N2 dissolved in blood
 problems with nerve conduction
 poor judgement, giddyness…

& when return to surface: N2(g) bubbles out of blood

 “the bends”
Air bag chemistry (ON YOUR OWN): exploiting a redox rxn

2 NaN3(s) → 2 Na(s) + 3 N2(g) …in the presence of SiO2 & KNO3,

which convert the reactive Na into
Your tasks: harmless salts.
1. Draw the Lewis structure of the azide anion, N3−. Include all equivalent
(most-stable) resonance structures.
2. Identify the oxidant and the reductant in the above reaction.
3. Answer Kotz Ch.10 #33: Find the mass of sodium azide required to fill
a 75.0 L airbag to 1.3 atm pressure of N2(g) at 25C.

Fig.10.6
 CHEM205 - GENERAL
Stoichiometry involving gases: cf
CHEMISTRY I Kotz 6th Ed. Ch.12 #62 FALL 2020
Department of Chemistry & Biochemistry

Dimethyldichlorosilane (CH3)2SiCl2 is a starting material used to make silicones,

which are polymeric substances used as lubricants, anti-stick agents and water-
proofing caulk. It is formed by the following reaction:
Si(s) + 2 CH3Cl(g) → (CH3)2SiCl2(g)
If you place 2.25g of solid silicon in a 6.56 L flask containing
CH3Cl at a pressure of 585 mm Hg at 25°C…
a) what mass of dimethyldichlorosilane can be formed?
b) what pressure would be exerted by this (CH3)2SiCl2(g) at 25°C?
c) what would be the total pressure in the flask after the reaction?

Additional questions:
1. What type of reaction is this? How can you tell?
2. How would you describe the reactants?
a) Element (metal, nonmetal, metalloid?) vs compound?
b) For compounds: ionic vs covalent? polar vs nonpolar?
c) Soluble in water?
Real gases behave non-ideally at times
(things to consider if/when we must be VERY accurate)

Must correct for non-ideal gas behavior for samples at

high pressure (smaller volume) and/or low temperature.
e.g., in compressed gas cylinders!
p.401
…WHEN INTERACTIONS ARE ACTUALLY SIGNIFICANT…

▪ HIGH P or SMALL V:
• Particles are closer together
• Polar molecules attract each other fairly strongly
• Nonpolar molecules’ interactions small but significant

▪ LOW TEMPERATURE:
• Particles are only moving slowly
• If not enough thermal energy to break away from
intermolecular interactions, gas will NOT behave ideally! Zumdahl
Fig.5.29
 CHEM205 - GENERAL
FALL 2020
CHEMISTRY I
Department of Chemistry & Biochemistry

To more accurately describe REAL GASES:

use van der Waals’ equation
Pressure term x Volume term = nRT

n 2a
( P + _____

V2
) x V - nb = nRT

J. van der Waals. 1837-1923,

Physics Prof., Amsterdam.
Measured P Measured V Nobel Prize 1910.

Compensate for “Volume of particles” correction

intermolecular forces… Real gas particles do NOT each have
Real gas particles “waste” some energy by zero volume
interacting with each other → Total volume occupied by
→ Observed pressure is lower real gas sample therefore
than if behaving ideally larger than predicted for
“ideal” gas
A real sample of Cl2 gas: CHEM205 - GENERAL
8.00 moles in a 4.00 L tank at 27.0°C FALL 2020
Department of Chemistry & Biochemistry
CHEMISTRY I
Ideally: P = nRT/V note: 8.00 mol is ~ 284 g of Cl2
P = (8.00 mol)(0.08206 Latmmol-1K-1)(300 K) / 4.00 L
= 49.2 atm  if the gas can behave ideally in this tank…
For “real” Cl2, experiments have shown: a = 6.49 atmL2/mol2
b = 0.0562 L/mol
n 2a
( P + _____

V2
) x V - nb nRT = 4.00L – (8.00mol x 0.0562 L/mol)
= 4.00L – (0.4496 L of matter)
= 3.550 L actual empty space…
=(8.00 mol)2 x (6.49 atmL2/mol2)
(4.00 L)2
=25.96 atm …interactions slow particles down…
…lost KE would be enough to cause this much more P
Thus: (P + 25.96 atm) x (3.550 L) = nRT
(3.550 L) P + 92.16 Latm = (8.00 mol)(0.08206 Latmmol-1K-1)(300 K)
(3.550 L) P + 92.16 Latm = 196.94 Latm
 P = 29.5 atm  the observed P is MUCH lower than ideal
 CHEM205 - GENERAL
Kinetic Molecular Theory of Gases
CHEMISTRY I
Department of Chemistry & Biochemistry
FALL 2020

THEORY PROPOSED (and accepted)

TO EXPLAIN OBSERVED BEHAVIOUR OF GASES:

1) Gases consist of particles (atoms, molecules), separated by

distances much greater than size of particles
2) Particles in constant, random, rapid motion…
…collide with each other and walls of container

3) Temperature determines the average kinetic energy of

particles (thus: same for any gas at same T!)
K.E. = ½m u 2
Average
mass velocity (speed)

ABOVE THREE POSTULATES: Exactly what we thought about to

determine when gases would behave “ideally”…
Velocities of N2 molecules at two temperatures

In a collection of molecules: DISTRIBUTION OF ENERGIES

▪ Some have high K.E., most have average, some have low K.E.
▪ Implies: not all molecules in a sample move at same speed…

Possible to calculate (not us…):

average or mean speed
u = n1 u1 + n2 u2 + n3 u3...
n 1 + n 2 + n 3…
 CHEM205 - GENERAL
Heavier molecules are slower at same temperature
CHEMISTRY I
Department of Chemistry & Biochemistry
FALL 2020

▪ In reality: velocity has direction (a vector quantity)

▪ Take SQUARE of average velocity then take square root
 removes sign: get directionless velocity
called “root mean square velocity” urms
• K.E. proportional to mean square velocity (urms2) & MASS
• If consider a mole of molecules:
KE = ½ m u 2 in 3D yields… urms = (3RT/M)1/2
where M = molar mass
the 3 comes from velocities in 3
dimensions…. Don’t worry about how.

TAKE HOME MESSAGE:

▪ lighter molecules travel
Fig.10.14 faster than heavier
molecules…
▪ relevant to things like
smelling odours!
Diffusion & Effusion: movement of gas molecules

1.Diffusion = mixing of gases due to Fig.

random molecular motions 10.16

air 1.Uncork
Heavier molecules diffuse/effuse more 2.Wait
slowly:
Rate for A = MB
Graham’s law Rate for B Br2(g)
MA

An exp’t to demonstrate different rates of motion: images from Zumdahl

glass tube air air
Cotton Cotton
soaked in soaked in
NH3(aq). HCl(aq).
NH3(g) escapes sol’n. NH3 HCl(g) escapes sol’n.
molecules lighter, so NH3(g) + HCl(g) → NH4Cl(s) HCl heavier, so diffuses
diffuses more quickly more slowly
See K.9th Fig.10.17
RateNH3/RateHCl = (MHCl / MNH3)1/2
= ( 36.46 g·mol-1 / 17.031 g·mol-1 )1/2
= 1.463  NH3 this much faster!
2. Effusion
= movement of gas through tiny holes
= faster for lighter molecules…
since they hit barrier more often!
WHY DOES IT HAPPEN?
molecules collide with container walls…
but if “hit” the hole: go through!
BALLOONS:
▪ molecules effuse through holes in rubber
▪ rate (= moles/time) is:
proportional to temperature
inversely proportional to molar mass.

He A He balloon deflates after a while See K.9th Fig.10.18

N2, • lighter He effuses out more rapidly than
O2 heavier N2 & O2 from air effuse in.
 CHEM205 - GENERAL
Identifying gases based on relative molecular speed
CHEMISTRY I
Department of Chemistry & Biochemistry
FALL 2020

The “Boltzmann plot” (molecules vs molecular speed at particular temp.) below

was prepared using the Simulation in the Gases chapter in
GeneralChemistryNow. Which species gives rise to which curve?

Species: A B C D
A. Xe O2 Ne He
B. Xe He Ne O2
C. He Ne O2 Xe
D. He O2 Ne Xe

See Kotz Sect.10.6 Review & Check #2

 CHEM205 - GENERAL
To end CHEM 205: Sustainability & greenI chemistry (1.2)
CHEMISTRY
Department of Chemistry & Biochemistry
FALL 2020

Case Study
Reducing greenhouse gases by capturing CO2(g) Ch.20 p.794
• Greenhouse gases: prevent heat leaving atmosphere  global warming
• Industrial activity produces more CO2 than plants (CO2 sinks) can consume
What if we could trap it via reaction, then bury it deep underground?
CO2(g) + (NH4)2CO3(s) + H2O(l) 2 NH4HCO3(s)

• Pass fossil-fuel • Pass gas stream • Slurry isolated & heated…

combustion gases through slurry • Reaction reverses to
through scrubber to • Captures CO2 but regenerate (NH4)2CO3 &
remove SO2 not N2 release pure CO2

Then: pure CO2 “geologically sequestered”…

• injected into porous rock layers, 2400m deep
• buried under impermeable rock layers
• trapped for 1000’s of years… ?....
Case Study p.794