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General Chemistry

Principles and Modern Applications


Petrucci Harwood Herring
9th Edition

Chapter 6: Gases
Dr. Chris Kozak
Memorial University of Newfoundland, Canada

General Chemistry: Chapter 6

Slide 1

Chapter 6 Learning Objectives

Gas Laws and using them to quantify gases


What are standard conditions, ie. STP?
Stoichiometric Reactions using Gases
Law of Partial Pressure for mixtures of gases
Determine and use the Kinetic Energy of gases
Are all gases ideal? Corrections for real gases
See my Teaching, Chem 1050 website for detailed
Learning Objectives.

www.chem.mun.ca/homes/cmkhome/CMKTeaching

General Chemistry: Chapter 6

Slide 2

6-1 Properties of Gases: Gas Pressure


Gas Pressure
P (Pa) =

Force (N)
Area (m2)

Liquid Pressure
P = g h d
g = 9.81 m/s2, h = height of column, d = density of liquid
General Chemistry: Chapter 6

Slide 3

Barometric Pressure
Standard
Atmospheric
Pressure
1 00 atm
1.00
760 mm Hg, 760 torr
101 325 kPa
101.325
kP
1.01325 bar
1013.25 mbar

General Chemistry: Chapter 6

Slide 4

Manometers

General Chemistry: Chapter 6

Slide 5

STP
Gas properties depend on conditions.
Define standard conditions of
temperature and pressure (STP).
P = 1 atm = 760 mm Hg
T = 0C

= 273.15 K

General Chemistry: Chapter 6

Slide 6

A Manometer Question
A liquid with d = 0.854 g mL-1 was used in an open-end
manometer to measure a gas pressure that was slightly greater
than atmospheric pressure, which was 745 mm Hg. In the
manometer, the liquid level was 17.5 mm higher in the open
arm than in the arm nearest the gas sample. What was the gas
pressure in torr?

General Chemistry: Chapter 6

Slide 7

6-3 The Ideal Gas Equation and the


General Gas Equation
Boyle
Boyles
s law
Charless law
Avogadros law

V 1/P
VT
Vn

nT
P

PV = nRT
RT
General Chemistry: Chapter 6

Slide 8

The Gas Constant

PV = nRT
PV
R=
nT
= 0.082057
0 082057 L atm mol-1 K-1
= 8.3145 m3 Pa mol-1 K-1
= 8.3145 J mol-1 K-1
General Chemistry: Chapter 6

Slide 9

The General Gas Equation


P 1V 1
P 2V 2
R=
=
n1T1
n2T2
If we hold the amount
and volume constant:

P1
T1

P2
T2

General Chemistry: Chapter 6

Slide 10

6-4 Applications of the Ideal Gas Equation


Molar Mass Determination

PV = nRT

and
PV =

m
RT
M

M=

m RT
PV

General Chemistry: Chapter 6

n=

m
M

Slide 11

Example 6-10
Determining a Molar Mass with the Ideal Gas Equation.
Propylene is an important commercial chemical
chemical. It is used
in the synthesis of other organic chemicals and in plastics
production. A glass vessel weighs 40.1305 g when clean,
dry and evacuated; it weighs 138.2410 g when filled with
water at 25C (=0.9970 g cm-3) and 40.2959 g when filled
with p
propylene
py
g
gas at 740.3 mm Hg
g and 24.0C. What is
the molar mass of propylene?
Strategy:
gy
Determine Vflask. Determine mgas. Use the Gas Equation.
General Chemistry: Chapter 6

Slide 12

Example 6-10
Determine
Vflask:
Vflask = mH2O dH2O = (138.2410 g 40.1305 g) (0.9970 g cm-3)
= 98.41
98 41 cm3 = 0.09841
0 09841 L
Determine mgas:
mgas = mfilled - mempty = (40.2959 g 40.1305 g)
= 0.1654 g

General Chemistry: Chapter 6

Slide 13

Example 5-6
6-10
Use the Gas
Equation:

PV = nRT
M=

PV =

m
RT
M

M=

m RT
PV

(0.1654 g)(0.08206 L atm mol-1 K-1)(297.2 K)


(0 9741 atm)(0
(0.9741
atm)(0.09841
09841 L)
M = 42.08 g/mol
H
C
H2C

CH3

General Chemistry: Chapter 6

Slide 14

Gas Densities
PV = nRT

and
PV =

m
m
,
n
=
d=
M
V
m
RT
M

m
MP
=d=
V
RT

General Chemistry: Chapter 6

Slide 15

6-5 Gases in Chemical Reactions


Stoichiometry relates gas quantities to
quantities of other reactants or products.
Ideal gas equation relates moles of gas
to V, T and P.
Law of combining volumes can be
developed using the gas law.

General Chemistry: Chapter 6

Slide 16

Example 6-12
Using the Ideal gas Equation in Reaction Stoichiometry
Calculations.
The decomposition of sodium azide, NaN3, at high
temperatures produces N2(g). Together with the necessary
devices to initiate the reaction and trap the sodium metal
formed, this reaction is used in air-bag safety systems.
What volume of N2(g), measured at 735 mm Hg
g and 26C,,
is produced when 70.0 g NaN3 is decomposed?
2 NaN3(s) 2 Na(l) + 3 N2(g)

General Chemistry: Chapter 6

Slide 17

Example 6-10
Determine moles of N2:
nN2 = 70 g NaN3

1 mol NaN3
65.01 g NaN3

3 mol N2
2 mol NaN3

= 1.62 mol N2

Determine volume of N2:


V=

nRT
P

(1.62 mol)(0.08206 L atm mol-1 K-1)(299 K)


((735 mm Hg)
g)

1.00 atm
760 mm H
Hg

= 41.1 L
General Chemistry: Chapter 6

Slide 18

6-6 Mixtures of Gases


Gas laws apply to mixtures of gases.
Simplest approach is to use
se ntotal, but....
b t
Partial pressure
Each component of a gas mixture exerts a
pressure that it would exert if it were in the
container
t i
alone.
l

ie. The total pressure exerted by a


mixture of gases is the sum of the
pressures exerted by each gas if it was
pure
General Chemistry: Chapter 6

Slide 19

Daltons Law of Partial Pressure

Pressure of each gas is proportional to the number of moles


of gas
The total pressure is the sum of the partial pressures of the
i di id l gases.
individual
General Chemistry: Chapter 6

Slide 20

Partial Pressure
Ptot = Pa + Pb +
Va = naRT/Ptot

and

Vtot = Va + Vb+

n
n RT/Ptot
Va
= a
= a
ntotRT/Ptot
ntot
Vtot
t t
t t
n
n RT/Vtot
Pa
= a
= a
ntotRT/Vtot
ntot
Ptot

Th Mole
M l Fraction
F ti
= a The

General Chemistry: Chapter 6

Slide 21

Partial Pressure
Partial pressure is the pressure of a component of
gas that contributes to the overall pressure.
Partial volume is the volume that a gas would occupy
at the total pressure in the chamber.
Ratio of partial volume to total volume
volume, or of partial
pressure to total pressure is the MOLE FRACTION.

General Chemistry: Chapter 6

Slide 22

Pneumatic Trough
Total pressure of wet gas (Pgas + PH2O) is equal to
atmospheric pressure (Pbar) if the water level is the same
inside and outside

Ptot = Pbar = Pgas + PH2O


General Chemistry: Chapter 6

Slide 23

Some Partial Pressure Problems


1. Suppose you want to fill a pressurized tank having a
volume of 4.00 L with oxygen-enriched air for use in diving,
and you want the tank to contain 50
50.0
0 g of O2 and 150 g of
N2. What will the total gas pressure have to be at 25 C?
2. A sample of oxygen is collected over water at 20 C
C and a
pressure of 738 torr. Its volume is 310 mL. (a) What is the
partial pressure of the oxygen? (b) What would be its
volume at STP when dry?

General Chemistry: Chapter 6

Slide 24

6-7 Kinetic Molecular Theory


Based on the following Model
Particles are point masses in
constant, random, straight line
motion.
Particles are separated by great
distances.
Collisions are rapid and elastic.
No force bet
between
een particles (e
(except
cept
during collisions).
Total
T t l energy remains
i constant.
t t
General Chemistry: Chapter 6

Slide 25

Pressure Assessing Collision Forces


Translational kinetic energy,

ek =

1
mu 2
2

N
V

Frequency of collisions,

v =u

Impulse or momentum
transfer
transfer,

I = mu

Pressure p
proportional
p
to
impulse times frequency

General Chemistry: Chapter 6

N
mu 2
V

Slide 26

Pressure and Molecular Speed


Three dimensional systems lead to: P =

1N
m u2
3V

is the simple average

urms =

u2

Not all molecules are travelling at the same speed.


Speed is here defined as the root mean square speed
speed,
urms.

General Chemistry: Chapter 6

Slide 27

Pressure
Assume one mole:

PV =

1
NAm u 2
3

PV = RT so:

3RT = N A m u 2

NAm = M:

3RT = M u 2

Rearrange:

u rms =

3RT
M

General Chemistry: Chapter 6

Slide 28

Distribution of Molecular Speeds

u rms =

3RT
M

Lighter gases have faster


speeds.
Increasing the temperature
increases their speed.

General Chemistry: Chapter 6

Slide 29

Temperature
Modify:

PV =

1
2
1
NAm u 2 = N A ( m u 2 )
3
3
2

PV=RT
PV
RT so:

RT =

Solve for ek:

ek =

2
N A ek
3

3 R
(T)
2 NA

Average kinetic energy is directly proportional to


temperature!
General Chemistry: Chapter 6

Slide 30

How does T really affect molecules?


Remember, ek = mu2 = (3/2)(R/NA)T.
Ch
Changes iin ttemperature
t
mean changes
h
iin th
the iintensity
t
it off
molecular motion, the translational kinetic energy!
Heat flow from a hot body to a cold body
body hot molecules
raise the temperature of cold ones by exchanging kinetic
energy through collisions. The exchange of heat/energy
continues
ti
until
til an equilibrium
ilib i
ttemperature
t
iis reached
h d allll
molecules possessing the same temperature/energy!
So, what about absolute zero? As T goes to 0 K, the
translational motion of all molecules stops!
The end of the Universe!
General Chemistry: Chapter 6

Slide 31

Kinetic Molecular Theory Problems


1. If it takes 1.25 minutes for 0.010 mol of He to
effuse
ff
through
th
h a smallll hole,
h l how
h
llong will
ill it ttake
k
for the same amount of ethane (C2H6) to effuse?

General Chemistry: Chapter 6

Slide 32

6-8 Gas Properties Relating to the


Kinetic-Molecular Theory
Diffusion
Net rate is proportional to
molecular speed.

Effusion
Eff i
A related phenomenon.

General Chemistry: Chapter 6

Slide 33

Grahams Law
rate of effusion of A (u rms ) A
3RT/M A
MB
=
=
=
rate of effusion of B (u rms ) B
3RT/MB
MA

Only for gases at low pressure (natural escape, not a jet).


Tiny orifice (no collisions)
Does not apply to diffusion.
Ratio used can be:
Rate of effusion (as above) Distances traveled by
molecules
Molecular speeds
Amounts of gas effused.
Effusion times
General Chemistry: Chapter 6

Slide 34

6-9 Real Gases


Compressibility factor PV/nRT = 1
Deviations occur for real gases
gases.
PV/nRT > 1 - molecular volume is significant.
PV/nRT < 1 intermolecular forces of attraction.

Red molecules attract the green


molecule making it exert less force on
the wall

General Chemistry: Chapter 6

Slide 35

Real Gases
At low Pressure, these gases
behave ideally
As pressure increases, the
molecules deviate from ideal
behaviour.
The heavier the gas, the more
weird it behaves
At a critical P and T, some
gases begin to behave like
liquids, but they are NOT
liquids but Supercritical Fluids!
General Chemistry: Chapter 6

Slide 36

van der Waals Equation

P+

n2a
V2

V nb

= nRT

Know why its important, but you dont need to use


it in this course
n2a/V2 takes into account intermolecular forces
nb describes the volume occupied by the n-molecules

General Chemistry: Chapter 6

Slide 37