Chem 16 General Chemistry 1

10 Gases

Dr. Gil C. Claudio

First Semester 2014-2015
Table of Contents

Contents
1 Gas Pressure and its Measurement

2 The Gas Laws

3 The Ideal Gas Law

4 Solving Gas Law Problems

5 Daltons Law of Partial Pressures

6 The Kinetic Molecular Theory of Gases

7 Real Gases: Deviations from Ideal Behavior

References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffy D. Madura, and Carey Bisonnette.
Chemistry: The Central Science, 13th ed., by Theodore L. Brown, H. Eugene
LeMay Jr., Bruce E. Bursten, Catherine J. Murphy, Patrick M. Woodward,
and Matthew W. Stoltzfus.
Characteristics of Gases
Some characteristics of gases
expands spontaneously to fill its container Vgas = Vcontainer
highly compressible
two or more gases form a homogeneous mixture regardless of the
identities or relative proportions of the gases
due to large distances between gas molecules

1 Gas Pressure and its Measurement

Pressure
Pressure is a force per unit area.
Applied to gases, pressure is most easily understood in terms of the
height of a liquid column that can be maintained by the gas.
1

 SI unit: N/m2 = Pa, kPa is more commonly used

1 bar = 105 Pa = 105 N/m2
Standard Atmosphere
The height of mercury in a barometer provides a measure of barometric
pressure.
density of mercury = 13.5951 g/cm3 (0 C), g = 9.80655 m/s2
P

ghd

= (9.80655 m/s2 )(0.7600 m)(1.35951 104 kg/m3 )

= 1.01325 105 kg/m-s2

1 atm

One standard atmosphere (atm) is defined to be exactly 101,325 Pa (or 101.325

kPa).
1 atm = 760 torr 760 mmHg
Some Common Pressure Units
Atmosphere
Millimeter of mercury
Torr
Pascal
Kilopascal
Bar
Millibar

atm
mmHg
Torr
Pa
kPa
bar
mbar

1 atm
760 mmHg
= 760 Torr
= 101,325 Pa
= 101.325 kPa
= 1.01325 bar
= 1013.25 mbar

2 The Gas Laws

Boyles Law
Boyles law states that tor a fixed amount of gas at a constant temperature,
the gas volume is inversely proportional to the gas pressure.
P

1
V

1
or
PV = constant
P
Because PV products of two states are equal to the same value,
V = constant

P1 V1 = P2 V2

Boyles Law Graph

commons.wikimedia.org/wiki/File:Boyles Law.svg

Charles Law
Charles Law state that the volume of a fixed amount of gas at constant
pressure is directly proportional to the Kelvin (absolute) temperature.
VT
V
= constant
T
For a transformation of a gas from state 1 to 2 at constant P
V = constant T

or

V
V1
= 2
T1
T2

Standard Conditions of T and P

Standard conditions of temperature and pressure (or STP).
0 C = 273.15 K
1 bar = 105 Pa (not 1 atm)
Avogadros Law
Avogadros law states that At a fixed temperature and pressure, the volume
of a gas is directly proportional to the amount of gas.
Vn

and

V = cn

where is c is the molar volume.

1 mol gas = 22.414 L (at 0 C, 1 atm) = 22.711 L (at STP)
Combined Gas Law
The combined gas law states that for a fixed quantity of gas
PV
P1 V1
= 2 2
T1
T2

n constant

3 The Ideal Gas Law

Summarizing the Three Laws
Changes in one variable have on the gas volume when the other two
variables are held constant.
1. Boyles law describes the effect of pressure, V 1/P
2. Charless law describes the effect of temperature, V T.
3. Avogadros law describes the effect of the amount of gas, V n.
The Ideal Gas Equation
Ideal Gas Equation
PV = nRT
P pressure in atm
V volume in L
n quantity in moles
T temperature in K
R universal gas constant. Some values of R
0.082057 L-atm/mol-K
0.083145 bar-L/mol-K
8.3145 J/mol-K
8.3145 Pa-m3 /mol-K
8.3145 kPa-L/mol-K
Calculations Using the Ideal Gas Equation
PHMB 10e, Examples 6.4 and 6.5, pp 205-206
1. What is the volume occupied by 13.7 g Cl2 (g) at 45 C and 745 mmHg?
2. What is the pressure, in kilopascals, exerted by 1.00 1020 molecules of
N2 in a 305 mL flask at 175 C?
ANSWERS:
1. 5.14 L
2. 2.03 kPa
The General Gas Equation
Applying the ideal gas law to a change of a gas from an initial to a final
state, we get the general gas equation
P f Vf
Pi Vi
=
ni Ti
n f Tf
At constant n, we get the combined gas law
P f Vf
Pi Vi
=
Ti
Tf

constant n

Effect of Temperature Changes on Pressure

BLBMWS 13e, Exercise 10.5, p 411
The gas pressure in an aerosol can is 1.5 atm at 25 C. Assuming that the
gas obeys the ideal-gas equation, what is the pressure when the can is heated
to 450 C?
ANSWER: 3.6 atm.
Combined Gas Law
BLBMWS 13e, Exercise 10.6, p 412
An inflated balloon has a volume of 6.0 L at sea level (1.0 atm) and
is allowed to ascend until the pressure is 0.45 atm. During ascent, the
temperature of the gas falls from 22 C to 21 . Calculate the volume of the
balloon at its final altitude.
ANSWER: 11 L

4 Solving Gas Law Problems

Determining a Molar Mass
PHMB 10e, Example 6-7, p 208
Propylene is an important commercial chemical (about ninth in the amount
produced among manufactured chemicals) used in the synthesis of other
organic chemicals and in production of plastics (polypropylene). A glass
vessel weighs 40.1305 g when clean, dry, and evacuated; it weighs 138.2410 g
when filled with water at 25.0 C (density of water = 0.9970 g/mL) and 40.2959
g when filled with propylene gas at 740.3 mmHg and 24.0 C. What is the
molar mass of propylene?
ANSWER: 42.08 g/mol
Calculating a Gas Density
PHMB 10e, Example 6-8, p 209
What is the density of oxygen gas O2 at 298 K and 0.987 atm?
ANSWER: 1.29 g/L
Law of Combining Volumes
Gay-Lussacs law of combining volumes states that, when compared at the
same temperature and pressure, the volumes of gases involved in a reaction are
in the ratio of small whole numbers.
Reaction Stoichiometry Calculations
PHMB 10e, Example 6-9, p 211
What volume of N2 , measured at 735 mmHg and 26 C, is produced when
75.0 g NaN 3 is decomposed?
2 NaN3 (s)

2 Na(l) + 3 N2 (g)

ANSWER: 43.9 L
Law of Combining Volumes
PHMB 10e, Example 6-10, p 212
Zinc blende ZnS is the most important zinc ore. Roasting (strong heating)
of ZnS in oxygen is the first step in the commercial production of zinc.
2 ZnS(s) + 3 O2 (g)

2 ZnO(s) + 2 SO2 (g)

What volume of SO2 (g) can be obtained from 1.00 L O2 (g) and excess ZnS(s)?
Both gases are measured at 25 C and 745 mmHg.
ANSWER: 0.667 L SO2 (g)

5 Daltons Law of Partial Pressures

Partial Pressure
A partial pressure is the pressure exerted by an individual gas in a mixture,
independently of other gases.
Each gas in the mixture expands to fill the container and exerts its own
partial pressure.
ntot RT
V
ntot RT
=
P

Ptot =

constant T and V

Vtot

constant T and P

Gas Mixtures
PHMB 10e, Example 6-11, p 213
What is the pressure, in bar, exerted by a mixture of 1.0 g H2 and 5.00 g He
when the mixture is confined to a volume of 5.0 L at 25 C?
ANSWER: 8.5 bar
Daltons Law of Partial Pressures
Daltons law of partial pressures states that in a mixture of gases, the total
pressure is the sum of the partial pressures of the gases present.
Ptot

=
=
=

PA + PB + . . .




RT
RT
nA
+ nB
+...
V
V
RT
RT
(n A + n B + . . . )
= ntot
V
V

The mole fraction x A of a gas in the mixture is

xA =

P
V
nA
= A = A
ntot
Ptot
Vtot

Mole Fractions and Partial Pressures

BLBMWS 13e, Exercise 10.11, pp 417-418
A study of the effects of certain gases on plant growth requires a synthetic
atmosphere composed of 1.5 mol % CO2 , 18.0 mol % O2 , and 80.5 mol % Ar.
1. Calculate the partial pressure of O2 in the mixture if the total pressure of
the atmosphere is to be 745 torr.
2. If this atmosphere is to be held in a 121-L space at 295 K, how many moles
of O2 are needed?
ANSWERS:
1. 134 torr
2. 0.880 mol
6

6 The Kinetic Molecular Theory of Gases

Kinetic Molecular Theory of Gases
The kinetic-molecular theory of gases is a model for describing gas
behavior. The assumptions are
1. Gases consist of large numbers of molecules that are in continuous, rapid,
random, straight-line motion.
2. The combined volume of all the molecules of the gas is negligible relative
to the total volume in which the gas is contained.
3. Attractive and repulsive forces between gas molecules are negligible.
4. Energy can be transferred between molecules during collisions but, as
long as temperature remains constant, the average kinetic energy of the
molecules does not change with time. Perfectly elastic collisions.
5. The average kinetic energy of the molecules is proportional to the
absolute temperature. At any given temperature, the molecules of all
gases have the same average kinetic energy.
Distribution of Molecular Speeds
The Maxwell distribution of speeds F (v)

3/2


M
Mv2
2
F (v) = 4v
exp
2RT
2RT
F (0) = 0
the probability density increases with the speed up to a maximum and
then declines.
Maxwell Boltzmann Distribution
Noble Gases

Probability density (s/m)

Maxwell-Boltzmann Molecular Speed Distribution for Noble Gases

0.004

0.003

He
Ne
40 Ar
132
Xe
20

0.002

0.001

500

1000

1500

2000

2500

Speed (m/s)
en.wikipedia.org/wiki/File:MaxwellBoltzmann-en.svg

Average Speeds
The most probable speed vmp is the speed at the maximum of F (v)
vmp =

2kB T
m

1/2

2RT
M

1/2

The mean speed hvi is calculated as the average of v using the probability
distribution F (v)




8RT 1/2
8kB T 1/2
=
hvi =
m
M
7

The root-mean-squared speed is

vrms

D E1/2  3k T 1/2  3RT 1/2

B
= v2
=
=
m
M

From these three calculations

vrms > hvi > vmp

Speeds of Gas Molecules

Various types of average speeds of gas molecules at 298 K

hvi
(m/s)
1769
444
379
672

vrms
(m/s)
1920
482
411
681

gas
H2
O2
CO2
CH4

vmp
(m/s)
1568
394
336
556

Mean Free Path

The mean free path is the average distance traveled between collisions
=

1
2d2

kB T

where

2d2 P

PNA
P
=
kB T
RT

where d is the collision diameter of an ideal gas molecule.

Mean Free Path of Oxygen
SAB 4e, Example 17.8, p 630
For oxygen at 25 C the collision diameter is 0.361 nm.
The mean free path at 1 bar pressure is 7.11 108 m, or 197 molecular
diameters.
The mean free path at 0.1 Pa pressure is 0.071 m (or 7.1 cm), or 1.97 108
molecular diameters
Distribution of Kinetic Energy
The kinetic energy distribution F () can be solved as
F () =

2
1/2 e/kB T
(kB T )3/2

and the average kinetic energy of an ideal gas molecule is

hi =

3
k T
2 B

The Kelvin temperature of a gas is directly proportional to the average

translational kinetic energy of its molecules.
Diffusion and Effusion
Diffusion refers to the spreading of a substance (usually a gas or liquid)
into a region where it is not originally present as a result of random molecular
motion.
Effusion is the escape of a gas through a tiny hole in its container.

Grahams Law
Grahams law states that the rates of effusion or diffusion of two different
gases are inversely proportional to the square roots of their molar masses. For
example

vrms,A
M
rate of effusion of A
=
= B
rate of effusion of A
vrms,B
MA
Can be applied to
molecular speeds, effusion rates, effusion times, distances traveled by
molecules, or amounts of gas effused
Gases Effusing Through an Orifice
PHMB 10e, Example 6-15, p 225
If 2.2 104 mol N2 (g) effuses through a tiny hole in 105 s, then how
much H2 (g) would effuse through the same orifice in 105 s?
ANSWER: 8.2 104 mol H2
Relating Effusion Times and Molar Masses
PHMB 10e, Example 6-16, p 225
A sample of Kr(g) escapes through a tiny hole in 87.3 s. The same amount
of an unknown gas escapes in 42.9 s under identical conditions. What is the
molar mass of the unknown gas?
ANSWER: 20.0 g/mol

7 Real Gases: Deviations from Ideal Behavior

The van der Waals Equation
The van der Waals equation is an equation of state for nonideal gases. It
includes correction terms to account for intermolecular forces of attraction and
for the volume occupied by the gas molecules themselves.


an2
P+ 2
V

(V nb) = nRT

b is the excluded volume per mole. It is (approximately) the volume that

one mole of gas occupies when it condenses to a liquid.
The proportionality constant a provides a measure of how strongly the
molecules attract each other.
Compressibility Factor
Real gases behave like ideal gases in the limits of low pressures and
high temperatures, but they deviate significantly at high pressures and low
temperatures. A convenient measure of the deviation from ideal gas behavior
is the compressibility factor
PV
Z=
nRT
At P 0, Z 1, ideal gas
At very high P, V > Videal because the molecules of the gas are pushed
closer together and a significant fraction of the volume is occupied by the
molecules themselves.
In some cases at low P, Z < 1 is possible due to IFA.

Compressibility Factor of Air

en.wikipedia.org/wiki/File:Compressibility Factor of Air 250 - 1000 K.png

VDW Constants and Compressibility Factors

at 10 bar and 300 K, PHMB 10e, Table 6.5, p 226
H2
He
N2
CO
O2
CH4
NF3
CO2
N2 O
C2 H6
NH3
SF6
C3 H8
SO2

a bar-L2 /mol2
0.2452
0.0346
1.37
1.472
1.382
2.303
3.58
3.658
3.852
5.58
4.225
5.58
9.39
7.857

b L/mol
0.0265
0.0238
0.0387
0.0395
0.0319
0.0431
0.0545
0.0429
0.0444
0.0651
0.0371
0.0651
0.0905
0.0879

Z
1.006
1.005
0.998
0.997
0.994
0.983
0.965
0.95
0.945
0.922
0.887
0.88
a
a

The van der Waals Equation

PHMB 10e, Example 6-17, pp 228-228
Use the van der Waals equation to calculate the pressure exerted by
1.00 mol Cl2 (g) confined to a volume of 2.00 L at 273 K. The value of
a = 6.49 L2 atm mol2 , and that of b = 0.0562 L mol1 .
ANSWER: 9.9 atm

10