Announcements

Final Exam: American Chemical Society standardized exam
The exam will have 70 questions to be taken in 120 minutes
The exam will have 70 questions to be taken in 120 minutes
Will count to 250 points
There is an ACS study guide on reserve in the library. 
 Chapter 5

The Gaseous State
 Operational Skills
Operational Skills
• Converting units of pressure.
• Using the empirical gas laws.
• Deriving empirical gas laws from the ideal gas law.
• Using the ideal gas law.
Using the ideal gas law.
• Relating gas density and molecular weight.
• Solving stoichiometry problems involving gases.
• Calc lating partial press res and mole fractions
Calculating partial pressures and mole fractions.
• Calculating the amount of gas collected over water.
• Calculating the rms speed of gas molecules.
• Calculating the ratio of effusion rates of gases.
• Using the van der Waals equation.
• In the first part of this chapter we will examine the
quantitative
tit ti relationships,
l ti hi or empirical
i i l laws,
l
governing gases. First, however, we need to
understand the concept of pressure.

Pressure, P
• The force exerted per unit area.
• It can be given by two
equations:
kg m kg
F   m 
P P  dgh m3 s2 m  s2
A  Pa (pascal)
•The SI unit for pressure is the pascal, Pa.
• A barometer is a device for measuring the 
pressure of the atmosphere.

• A
A manometer
manometer is a device for measuring the 
is a device for measuring the
pressure of a gas or liquid in a vessel.
Boyle’s Law
• The volume of a sample of gas at constant 
te pe atu e a es e se y t t e app ed
temperature varies inversely with the applied 
pressure.
1
V
P
• The mathematical relationship:

PV  constant
• In equation form: 
In equation form: PiVi  PfVf
When a 1.00-g sample of
O2 gas at 0°C
0 C is placed in
a container at a pressure
of 0.50 atm,, it occupies
p a
volume of 1.40 L.

When the pressure on the

O2 is
i doubled
d bl d to t 1.0
1 0 atm,
t
the volume is reduced to
0 70 L
0.70 L, half the original
volume.
 A Problem to Consider
• A volume of oxygen gas occupies 38.7 mL at 
751 mmHg and 21°C. What is the volume if the 
pressure changes to 359 mmHg while the 
temperature remains constant?

Vi = 38.7 mL Vf = ?
Pi = 751 mmHg Pf = 359 mmHg
Ti = 21°C Tf = 21°C

PiVi
Vf 
Pf
Vi = 38.7 mL Vf = ?
Pi = 751 mmHg Pf = 359 mmHg
Ti = 21°C Tf = 21°C

PiVi
Vf 
Pf

(751 mmHg)(38.7
mmHg)(38 7 mL)
Vf 
(359 mmHg)
= 81.0 mL
(3 significant figures)
Charles’s Law
• The volume of a sample of gas at constant pressure is 
The volume of a sample of gas at constant pressure is
directly proportional to the absolute temperature (K).

• The mathematical relationship:

• In equation form:
In equation form: V T
V
 constant
T
Vi Vf

Ti T f
A balloon was immersed
in liquid nitrogen and is
shown immediately after
As the air inside
being removed.
removed It warms,, the balloon
shrank because air expands to its
inside contracts in orginial size.
volume.
 A Problem to Consider
• You prepared carbon dioxide by adding HCl(aq) 
p,
to marble chips, CaCO 3. According to your 
g y
calculations, you should obtain 79.4 mL of CO2 at 
0°C and 760 mmHg. How many milliliters of gas 
g y g
would you obtain at 27°C?

Vi = 79.4 mL Vf = ?
Pi = 760 mmHg Pf = 760 mmHg
Ti = 0°C = 273 K Tf = 27°C = 300. K

T fVi
Vf 
Ti
Vi = 79.4 mL Vf = ?
Pi = 760 mmHg Pf = 760 mmHg
Ti = 0°C = 273 K Tf = 27°C = 300. K

T fVi
Vf 
Ti
(300. K)(79.4 mL)
Vf 
(273 K)

= 87.3 mL
(3 significant figures)
Gay‐Lussac’s Law:
• The pressure exerted by a gas at constant 
o u e s d ect y p opo t o a to ts abso ute
volume is directly proportional to its absolute 
temperature. 

P α Tabs ((constant moles and V))

or

Pf
Tf  Pi
Ti
 A Problem to Consider
• An aerosol can has a pressure of 1.4 atm at 
25°C
25 C. What pressure would it attain at 
What pressure would it attain at
1200°C, assuming the volume remained 
constant?
Pf Pi
g
using 
Tf Ti
Pi Tf
Pf  Ti  (1.4 atm )(1473 K )
( 298 K )

Pf  6.9atm
t
Combined Gas Law
• The volume of a sample of gas at constant pressure is 
inversely proportional to the pressure and directly 
yp p p y
proportional to the absolute temperature.

• The mathematical relationship:

T
• In equation form: V
P
•

PV
 constant
T
PiVi PfVf

Ti Tf
 A Problem to Consider
• Divers
Divers working from a North Sea drilling platform 
working from a North Sea drilling platform
experience pressure of 5.0 × 101 atm at a depth of 
5 0 × 102 m. If a balloon is inflated to a volume of 
5.0 × m If a balloon is inflated to a volume of
5.0 L (the volume of the lung) at that depth at a 
water temperature of 4°C
water temperature of 4 C, what would the 
what would the
volume of the balloon be on the surface (1.0 atm 
pressure) at a temperature of 11°C?
pressure) at a temperature of 11 C?

Vi = 5.0 L Vf = ?
Pi = 5.0 × 101 atm Pf = 1.0 atm
Ti = 4°C = 277 K Tf = 11°C = 284 K
Vi = 5.0 L Vf = ?
Pi = 5.0 × 101 atm Pf = 1.0 atm
Ti = 4°C = 277 K Tf = 11°C = 284 K

T f PiVi
Vf 
Ti Pf
((284 K)(5.0
)( x 10 1 atm)(5.0
)( L))
Vf 
(277 K)(1.0 atm)
= 2.6 x 102 L
(2 significant figures)
 • Avogadro’s Law
• Equal volumes of any two gases at the same 
Equal volumes of any two gases at the same
temperature and pressure contain the same 
number of molecules. V α n
number of molecules. V α
Standard Temperature and Pressure (STP)
The reference condition for gases, chosen by convention to be 
g , y
exactly 

Temperature = 0°C
Pressure = 1 atm
molar volume, Vm = 22.4 L/mol
Ideal Gas Law
• The ideal g
gas law
is given by the
q
equation
PV=nRT

• The molar gas

constant,
t t R, R is
i the
th
constant of
proportionality
ti lit
that relates the
molar
l volumel off a
gas to T/P
• The numerical value of R can be derived using 
g
Avogadro’s law, which states that one mole of 
any gas at STP will occupy 22.4 liters.

R VP
nT

R (22.4 L)(1.00 atm)

(1 00 mol)(273 K)
(1.00

 Latm
t
0 0821 molK
0.0821
 A Problem to Consider
• A 50.0‐L cylinder of nitrogen, N2, has a pressure of 
17.1 atm at 23°C. What is the mass of nitrogen in 
the cylinder?

V = 50.0
50 0 L PV
P = 17.1 atm n
RT
T = 23
23°C
C = 296 K
(17.1 atm)(50.0 L)
n
 L  atm 
 0.08206 (296 K)
 mol  K 

mass  35.20 mol

28.02
28 02 g mass = 986 g
mol (3 significant figures)
 Homework
• How many moles of gas are in a gas sample occupying 1.77 L at 623 
How many moles of gas are in a gas sample occupying 1 77 L at 623
mmHg and 298 K? (1atm = 760 mmHg, R =0.0821 L.atm/mol.K)

a)) 3.70 mol
b) 0.0593 mol
c) 0.00487 mol
d) 16.9 mol
e) 45.1 mol
 Molecular Weight Determination
Molecular Weight Determination
Recall the relationship between moles and 
Recall the relationship between moles and
mass.

moles  mass
molecular mass
or

n m
Mm
 Molecular Weight Determination
Molecular Weight Determination
• If
If we substitute this in the ideal gas equation, 
we substitute this in the ideal gas equation
we obtain
PV  m
( M m )RT
If we solve this equation for the molar mass,
we obtain

mRT
Mm 
PV
 A Problem to Consider
A Problem to Consider
• A
A 15.5 gram sample of an unknown gas 
15 5 gram sample of an unknown gas
occupied a volume of 5.75 L at 25°C and a 
pressure of 1 08 atm Calculate its molar
pressure of 1.08 atm. Calculate its molar 
mass.
mRT
Since M m 
PV
Latm
L
(15 5 g)(0.0821
(15.5 )(0 0821 mol K )(298 K)
then Mm 
(1.08 atm)(5.75 L)
M m  61.1 g/mol
 Homework
• A 500.0‐mL flask containing a sample of octane (a 
component of gasoline) is placed in a boiling water 
b th i D
bath in Denver, where the atmospheric pressure is 634 
h th t h i i 634
mmHg and water boils at 95.0°C. The mass of the 
vapor required to fill the flask is 1 57 g What is the
vapor required to fill the flask is 1.57 g. What is the 
molar mass of octane? (Note: The empirical formula of 
octane is C4H9.) What is the molecular formula of 
octane?

g
M m  114
mol
(3 significant figures)
 Density Determination
Density Determination
• If
If we look again at our derivation of the 
we look again at our derivation of the
molecular mass equation,

PV  m
( M m )RT
we can solve for m/V, which represents density.

m PM m
D
V RT
 A Problem to Consider
A Problem to Consider
Calculate the density of ozone, O
Calculate the density of ozone O3 (Mm = 
(Mm =
48.0g/mol), at 50°C and 1.75 atm of pressure.

PM m
Since D 
RT
(1.75 atm)(48.0 g/mol)
then D Latm
L
(0 0821 mol
(0.0821 K )(323 K)

D  3.17 g/L
 A Problem to Consider
What is the density of methane gas (natural 
gas), CH4, at 125
gas), CH , at 125°C
C and 3.50 atm?
and 3.50 atm?
Mm = 16.04 g/mol MmP
d
P=3 3.50
50 atm RT
T = 125°C = 398 K

g
(16.04 )(3.50 atm) g
d mol d  1.72
L  atm  L

 0.08206 (398 K) (3 significant figures)
 mol  K 
Fig 5.13  The Production of O2 by Thermal 
Decomposition of KCIO3
Decomposition of KCIO
 Stoichiometry Problems Involving Gas 
V l
Volumes
• Consider the following reaction,
reaction which is often
used to generate small quantities of oxygen.

2 KClO 3 (s)  2 KCl(s)  3 O 2 (g )

• Suppose you heat 0.0100 mol of potassium chlorate, 
KClO3, in a test tube. How many liters of oxygen can you 
i t tt b H lit f
produce at 298 K and 1.02 atm? 
 Stoichiometry Problems 
Involving Gas Volumes
l l
• First
First we must determine the number of 
we must determine the number of
moles of oxygen produced by the reaction.

3 mol O 2
0.0100 mol KClO 3 
2 mol KClO 3
 0.0150 mol O 2
 Stoichiometry Problems Involving Gas 
Volumes
l
• Now
Now we can use the ideal gas equation to 
we can use the ideal gas equation to
calculate the volume of oxygen under the 
conditions given
conditions given.
nRT
V
P
Latm
V ((0.0150 mol O 2 )( 0.0821 mol
1.02 atm
K )(
)(298 K))

V  0.360
0 360 L
 Homework

When a 2.0‐L bottle of concentrated HCl was 
spilled, 1.2 kg of CaCO
ill d 1 2 k f C CO3 was required to 
i d
neutralize the spill. What volume of CO2 was 
released by the neutralization at 735 mmHg 
l db h li i 735 H
and 20.°C?

= 2.98 × 102 L
(2 significant figures)
 Partial Pressures of Gas Mixtures
Partial Pressures of Gas Mixtures
• Dalton’s
Dalton s Law of Partial Pressures:
Law of Partial Pressures: the sum of 
the sum of
all the pressures of all the different gases in a 
mixture equals the total pressure of the
mixture equals the total pressure of the 
mixture.  

Ptot
t t  Pa  Pb  Pc  ....
 Partial Pressures of Gas Mixtures
Partial Pressures of Gas Mixtures
• The
The composition of a gas mixture is often 
composition of a gas mixture is often
described in terms of its mole fraction.
– The mole fraction,  , of a component gas is
the fraction of moles of that component in the
total moles of gas mixture.
mixture

n A PA
 A  Mole i off A 
M l fraction
f 
n tot Ptot
 Partial Pressures of Gas Mixtures
Partial Pressures of Gas Mixtures
• The
The partial pressure of a component gas, 
partial pressure of a component gas “A”
A , 
is then defined as
PA   A  Ptot
– Applying
A l i thisthi conceptt to
t the
th ideal
id l gas equation,
ti
we find that each gas can be treated
independently.
independently

PA V  n A RT
 A problem to consider

A 100.0‐mL sample of air exhaled from the lungs is 
analyzed and found to contain 0 0830 g N2, 0.0194 
analyzed and found to contain 0.0830 g N 0 0194
g O2, 0.00640 g CO2, and 0.00441 g water vapor at 
35°C
35 C. What is the partial pressure of each 
What is the partial pressure of each
component and the total pressure of the sample?
  1 mol N 2  L  atm 
 0.0830 g N 2  0.08206 308 K 
 28 01 g N 2
28.01  mol  K 
PN2   0.749 atm
 
100.0 mL  13L 
 10 mL 
 1 mol O 2  L  atm 
 0.0194 g O 2  0.08206 308 K 
 32.00 g O 2  mol  K 
PO2   0.153 atm
 
100.0 mL  13L 
 10 mL 
 1 mol CO 2  L  atm 
 0.00640 g CO 2  0.08206 308 K 
 44 01 g CO 2 
44.01 moll  K 
PCO2   0.0368 atm
 
100.0 mL  13L 
 10 mL 
 1 mol H 2 O  L  atm 
 0.00441 g H 2 O  0.08206 308 K 
 18.01 g H O  mol  K 
PH2O 
2
 0.0619 atm
 1L 
100.0 mL  3 

 10 mL 
 PN2  0.749 atm
PO2  0.153 atm
PCO2  0.0368
0 0368 atm
PH2O  0.0619 atm

P  PN2  PO2  PCO2  PH2O

P = 1.00 atm
 A Problem to Consider
• The partial pressure of air in the alveoli (the air sacs in the 
lungs) is as follows: nitrogen, 570.0 mmHg; oxygen, 103.0 
mmHg; carbon dioxide, 40.0 mmHg; and water vapor, 47.0 
mmHg. What is the mole fraction of each component of 
the alveolar air?
h l l i?

P  PN2  PO2  PCO2  PH2O

570.0 mmHg
103.0 mmHg
40.0 mmHg
47 0 mmHg
47.0 H
P = 760.0 mmHg
Mole fraction of N2 Mole fraction of O2
570.0 mmHg 103.0 mmHg
 
760.0 mmHg 760.0 mmHg
Mole fraction of CO2 Mole fraction of H2O
40.0 mmHg 47.0 mmHg
 
760.0 mmHg 760.0 mmHg
Mole fraction N2 = 0.7500

Mole fraction O2 = 0.1355

Mole fraction CO2 = 0.0526

Mole fraction O2 = 0.0618

 Collecting Gases “Over Water”
• A different situation applies when you collect 
gases over water.  

– As
A gas bbubbles
bbl ththrough
h th
the water,
t th the
gas becomes saturated with water
vapor.

– The partial pressure of the water in this

p
“mixture” depends only
y on the
temperature.
 A Problem to Consider
• Suppose a 156 mL sample of H2 gas was collected over 
water at 19oC and 769 mm Hg. What is the mass of H2
collected? 
ll t d?
– First, we must find the partial pressure of
the dry H2.
PH  Ptot  PH
2 2 0
– Table 5.6 lists the vapor pressure of water
at 19oC as 16.5 mm Hg.

PH  769 mm Hg - 16.5 mm Hg
2

PH  752 mm Hg
2
 A Problem to Consider

• Now
Now we can use the ideal gas equation, along 
we can use the ideal gas equation along
with the partial pressure of the hydrogen, to 
determine its mass
determine its mass.

PH  752 mm Hg  7601mm
2
atm
H  0.989 atm
Hg
V  156 mL  0.156 L
T  (19  273)  292 K
n?
 A Problem to Consider
• From the ideal gas law, PV = nRT, you have

PV (0.989 atm)(0.156 L)
n  Latm
RT (0.0821 mol K )( 292 K )

n  0.00644 mol
– Next,convert
Next convert moles of H2 to grams of H2.
2.02 g H 2
0 00644 mol H 2 
0.00644  0.0130
0 0130 g H 2
1 mol H 2
 Homework
• You prepare nitrogen gas by heating ammonium
nitrite:
( )  N2(g) + 2H
NH4NO2(s)  ( ) + 2H2O(l)
If you collected the nitrogen over water at 23°C and
727 mmHg, g, how manyy liters of ggas would yyou obtain
from 5.68 g NH4NO2?

• An excess of sodium hydroxide is treated with 1.2 L of

dryy hydrogen
y g chloride ggas measured at STP. What is
the mass of sodium chloride formed?
 Kinetic-Molecular Theory
(Ki ti Theory)
(Kinetic Th )
A theory,
y developed
p by ypphysicists,
y
that is based on the assumption that
aggas consists of molecules in
constant random motion.

Kinetic energy is related to the mass

y
and velocity:
1
m = mass EK  mv 2

v = velocity 2
 Postulates of the Kinetic Theory
1. Gases are composed of molecules whose sizes are negligible.

2. Molecules move randomly in straight lines in all directions 
and at various speeds.
and at various speeds.

3. The forces of attraction or repulsion between two molecules 
(i t
(intermolecular forces) in a gas are very weak or negligible, 
l l f )i k li ibl
except when the molecules collide.
4. When molecules collide with each other, the collisions are 
elastic.
5. The average kinetic energy of a molecule is proportional to 
the absolute temperature.
p
Each of the gas laws can be derived from
the postulates.

For the ideal gas law:

P  frequency of collision x average force

The average force depends on the mass of the
molecules, m, and its average speed, u; it
d
depends
d on momentum,t mu.

The frequency of collision is proportional to

the average speed, u, and the number of
molecules,, N,, and inversely
y proportional
p p to the
volume, V.

 1 
P   u   N   mu
 V 
Rearranging this relationship gives

PV  Nmu
N 2

The average kinetic energy of a

molecule of mass m and average speed
u is 1/2mu2.

Thus PV is proportional to the average

kinetic energy of the molecule.
• However
However, the average kinetic energy is also 
the average kinetic energy is also
proportional to the absolute temperature 
and the number of molecules N is
and the number of molecules, N, is 
proportional to moles of molecules. We now 
have

PV  nT
• Inserting the proportionality constant, R,
gives

PV  nRT
RT
Molecular Speeds
• According
According to kinetic theory, molecular speeds vary 
to kinetic theory molecular speeds vary
over a wide range of values. The distribution 
depends on temperature, so it increases as the
depends on temperature, so it increases as the 
temperature increases.
Root‐Mean
Root Mean Square (rms) Molecular Speed, u
Square (rms) Molecular Speed, u

3RT
u
Mm
• A type of average molecular speed, equal to the 
speed of a molecule that has the average molecular 
ki i
kinetic energy
• When using the equation
When using the equation

R = 8.3145 J/(mol 
/( l K))

• T must be in Kelvins
• Mm must be in kg/mol
must be in kg/mol
 Problem to consider
• What is the rms speed of carbon dioxide 
molecules in a container at 23°C?
molecules in a container at 23°C?

T = 23
23°C
C = 296 K 3RT
u rms 
CO2 molar mass = Mm
0.04401 kg/mol
g
  kg  m 
2
 
3 8.3145 s 296 K 
2
Recall
kg  m 2 mol  K 
J  
2  
u s 
rms
 kg 
 0.04401 
 mol 

2
m
u rms  1.68x10 5 2
s
m
u rms  4.10 x10
2
s
• Maxwell 
predicted the 
distributions 
of molecular
of molecular 
speeds at 
various 
various
temperatures. 
The graph 
shows 0°C and 
500°C.
Diffusion
• The process whereby a gas spreads out through 
The process whereby a gas spreads out through
another gas to occupy the space uniformly
• Below NH
Below NH3 diffuses through air. The indicator 
diffuses through air The indicator
paper tracks its progress.
Effusion
p y g g
• The process by which a gas flows through a small 
hole in a container. A pinprick in a balloon is one 
example of effusion.
Graham’s Law of Effusion

• At
At constant temperature and pressure, the 
constant temperature and pressure the
rate of effusion of gas molecules through a 
particular hole is inversely proportional to
particular hole is inversely proportional to 
the square root of the molecular mass (and 
molar mass) of the gas
molar mass) of the gas.

1
rate of effusion of molecules 
Mm
 A problem to consider
• Both hydrogen and helium have been used as 
the buoyant gas in blimps. If a small leak were 
t
to occur, which gas would effuse more rapidly 
hi h ld ff idl
and by what factor?

1
Rate
R t H2 2.016
2 016 4.002
4 002
 
Rate He 1 2.016
4.002
Hydrogen will diffuse more quickly by a
factor of 1.4.
Real Gases
• At high pressure the relationship between 
At high pressure the relationship between
pressure and volume does not follow Boyle’s 
law. This is illustrated on the graph below.
law. This is illustrated on the graph below.
At high pressure, some of the assumptions of 
At high pressure some of the assumptions of
the kinetic theory no longer hold true:

1. At high pressure, the volume of the gas 
molecule (Postulate 1) is not negligible.

2. At high pressure, the intermolecular forces 
(Postulate 3) are not negligible.
(Postulate 3) are not negligible.
Van der Waals Equation
• An equation that is similar to the ideal gas 
An equation that is similar to the ideal gas
law, but which includes two constants, a and 
b to account for deviations from ideal 
b, to account for deviations from ideal
behavior.

The term V becomes (V – nb).

The term P becomes (P + n2a/V2).
Values for a and b
Values for a and b are found in Table 5.7
are found in Table 5 7
 n a
2
P  V  nb   nRT
 2 
 V 
 Problem to consider
• Use the van der Waals equation to calculate 
the pressure exerted by 2.00 mol CO2 that has 
a volume of 10.0 L at 25°C. Compare this with 
value with the pressure obtained from the 
ideal gas law.

n = 2.00 mol For CO2:

V = 10.0 L a = 3.658 L2 atm/mol2
T = 25°C = 298 K b = 0.04286 L/mol
 n = 2.00 mol Ideal gas law:
V = 10.0 L
T = 25°C = 298 K nRT
P
V

 L  atm 
2.00
2 00 mol  0.08206
0 08206 (298 K)
 mol  K 
P
10.0 L 
= 4.89 atm
(3 significant figures)
 n = 2.00 mol For CO2:
V = 10.0 L a = 3.658 L2 atm/mol2
T = 25°C = 298 K b = 0.04286 L/mol
nRT n2a
P  2
V  nb  V
 L  atm   L2
 atm 
2.00 mol  0.08206 298 K  2.00 mol   3.658 
2

 mol  K   mol 
2
P 

10.0 L  2.00 mol 0.04286
L 

10.0 L 2
 mol 

P  4.933 atm  0.146 atm

Pactual = 4.79
4 79 atm
t
(3 significant figures)