Chapter 5

The Gaseous State

Elements that exist as gases at 250C and 1 atmosphere
Nobel gases are the only monoatomic species;
the other elements exist as diatomic
molecules. Ozone O3 is also a gas

• Gases assume the volume and shape of their containers.

• Gases will mix evenly and completely when confined to the same
container.
• Gases have much lower densities than liquids and solids. They are
compressible
• Pressure, volume, temperature, and amount are related.
HCN is a deadly poison. CO, H2S, NO2, O3, and SO2 are less toxic. He and Ne are
chemically inert.
 5.1 Gas Pressure and Its Measurement
Pressure force
The force exerted per unit area of surface. Pressure  area
Pascal (very small)
The SI unit for pressure; kg/(m·s2). 1 pascal (Pa) = 1 N/m2
1.0 N is the force required to accelerate 1.0 kg 1.0 m/s2

• Earth exerts gravitational force on everything with mass that is

on it or near it
– Weight measure of gravitational force that earth exerts
on objects with mass
• What we call weight is gravitational force acting on object

Atmospheric Pressure
 Resulting force per unit area
 When earth's gravity acts on molecules in air
 Pressure due to air molecules colliding with object
 A barometer is a device for
measuring the pressure of the
atmosphere.
 A manometer is a device for
measuring the pressure of a
gas or liquid in a vessel.
Standard Atmospheric Pressure
1.00 atm is equal to the pressure that support a
column mercury exactly 760 mm high at 0oC at sea
level
Mercury barometer
760 mm Hg = 760 torr; 101.325 kPa = 1.01325 bar
 A manometer is a device to measure the pressure of gases other
than atmosphere. Using Hg as the working fluid because it has a
very high density (13.6 mg/l).
 The general Relation between the
pressure P and the height h of a liquid
column in a barometer or monometer

P = gdh
 Where g is the constant acceleration of gravity: 9.81 m/s2.
 d: the density of liquid in the manometer, P is in pascals.
Example: Suppose that you set up two barometers. In one of the
barometers you use mercury, and in the other you use water. Which
of the barometers would have a higher column of liquid, the one
with Hg or H2O? Explain your answer.
The water column would be higher because its density is less by a
factor equal to the density of mercury to the density of water.

Example: The pressure of a gas in a flask is measured to be

797.7 mm Hg using a mercury-filled manometer. What is the
pressure in pascals and atmospheres?

797.7 mm Hg x 1 atm/760mmHg = 1.050 atm

1.050 atm x 1.01325 x 105 Pa = 1.064 x 105 Pa

HW; A gas in a container had a measured pressure of 57 kPa. Calculate the pressure in
units of atm and mmHg.
 5.2 Empirical Gas Laws
 All gases behave quite simply with respect to temperature,
pressure, volume, and molar amount. By holding two of
these physical properties constant, it becomes possible to
show a simple relationship between the other two properties.
At normal atmospheric pressure, the
volume of the gas is 100 mL. When
pressure is doubled, the volume is
halved. When pressure is tripled, the
volume decreases to one-third.
Boyle’s Law When a 1.00-g
The volume of a sample of gas at sample of O2 gas
at 0°C is placed
constant temperature varies in a container at a
inversely with the applied pressure. pressure of 0.50
atm, it occupies a
The mathematical relationship: volume of 1.40 L.
1
V 
P
In equation form: When the pressure
PV  constant on the O2 is
doubled to 1.0 atm,
the volume is
Pf V f  PV
i i reduced to 0.70 L,
half the original
volume.
Plot of volume vs. Plot of 1/V vs. pressure
pressure for a sample of for the same sample.
oxygen.
Example: A volume of air occupying 12.0 dm3 at 98.9 kPa is
compressed to a pressure of 119.0 kPa. The temperature remains
constant. Determine the new volume.

Vi = 12.0 dm3 Vf = ?
Pi = 98.9 kPa Pf = 119.0 kPa

PV Pi 98.9 kPa
Vf  i i V f  Vi   12.0 dm 
3
= 9.97 dm 3
Pf Pf 119.0 kPa

Example: A sample of chlorine gas occupies a volume of 946 mL at a pressure

of 726 mmHg. What is the pressure of the gas (in mmHg) if the volume is
reduced at constant temperature to 154 mL?
P2 = 4459.7 mm Hg
 Charles’s Law
The volume of a sample of gas at constant pressure is directly
proportional to the absolute temperature (K).
In equation form: V
 constant
T
Vi V f

Ti T f

A balloon was immersed in As the air inside warms, the

liquid nitrogen (black container) balloon expands to its original
and is shown immediately after size.
being removed. It shrank because
air inside contracts in volume.
A graph of V versus T is linear. Note that all lines cross zero
volume at the same temperature, −273°C where the volume is
zero (If the substance remain gas at this temp then the volume
will be zero which is not possible because all gases liquefy
before this temp and Charles’s law does not apply to liquids.
A 1.0-g sample of O2 at 100 K and When the absolute temperature of
1.0 atm of pressure occupies a the gas is doubled to 200 K, the
volume of 0.26 L. volume of O2 doubles to 0.52 L.

Example: If the total volume of oxygen that can be obtained from a

particular tank at 1.00 atm and 21oC is 785 L (including the volume
remaining in the tank). What would be this volume of oxygen if the
temperature had been 28oC?

Vf = 804 L
Combined Gas Law
The volume of a certain amount of gas at constant amount of gas
is proportional to the absolute temperature divided by the
pressure. T
The mathematical relationship: V 
P
In equation form:  All T 's must be in K
PV  Value of P and V can be any units as long as
 constant they are the same on both sides
T
 Gives all relationships needed for fixed
Pf V f PV
i i amount of gas under two sets of conditions
=
Tf Ti
Q5-1: What will be the final pressure of a sample of
nitrogen gas with a volume of 950. m3 at 745 torr and
25.0 °C if it is heated to 60.0 °C and given a final volume
of 1150 m3? P = 688 torr
2
Example: Anesthetic gas is normally given to a patient when
the room temperature is 20.0 °C and the patient’s body
temperature is 37.0 °C. What would this temperature
change do to 1.60 L of gas if the pressure and mass stay
the same?
 What do we know? V1 V2
 P and n are constant =
 So combined gas law simplifies to
T1 T2

V1T2 1.60 L ´ 310.15 K

V2 = =
T1 293.15 K

V2 = 1.69 L

16
Example: A sample of carbon monoxide gas occupies 3.20 L at 125 0C. At what
temperature will the gas occupy a volume of 1.54 L if the pressure remains constant?
V1/T1 = V2/T2
V1 = 3.20 L V2 = 1.54 L

T1 = 398.15 K T2 = ?
V2 x T1
T2 = = 191.6 K
V1

Example: If a sample of air occupies 500. mL at 273.15 K and 1 atm, what is the
volume at 85.0 °C and 560. torr? Ans: V2= 890.0ml

Ex: According to the Dumas method of determining %N in an organic compound,

39.8 mg of caffeine gives 10.1 cm3 of nitrogen gas at 23°C and 746 mmHg.
Determine the volume of nitrogen at 0°C and 760mmHg.
Ti  (23  273) K = 296 K
T f  (0  273) K = 273 K Ans: Vf= 9.14cm3
Vi  10.1 cm3 Pi  746 mmHg Ti  296 K
Vf  ? Pf  760 mmHg T f  273 K
Concept Check 5.2
To conduct some experiments, a 10.0-L flask equipped
with a movable plunger, as illustrated here, is filled with
enough H2 gas to come to a pressure of 20 atm.
a. In the first experiment, we decrease the
temperature in the flask by 10°C and then
increase the volume. Predict how the pressure in
the flask changes during each of these events
and, if possible, how the final pressure compares
to your starting pressure.
b. Once again we start with the pressure in the flask at 20 atm. The flask
is then heated 10°C, followed by a volume decrease. Predict how the
pressure in the flask changes during each of these events and, if possible,
how the final pressure compares to your starting pressure.

a. Decreasing the temperature at a constant pressure results in a decrease

in volume. Subsequently increasing the volume at a constant
temperature results in a decrease in pressure.
b. Increasing the temperature at a constant pressure results in an increase
in volume. Subsequently decreasing the volume at a constant
temperature results in an increase in pressure.
Avogadro’s Law
 Equal volumes of any two gases at the same temperature and
pressure contain the same number of molecules.
 Volume of a gas is directly proportional to its number of moles, n

V a number of moles (n)

V = constant x n
At constant temperature and Pressure
V1/n1 = V2/n2
Standard Temperature and Pressure (STP)
The reference conditions for gases chosen by convention to be
exactly 0°C and 1 atm pressure.
The molar volume of a gas at STP is 22.4 L/mol.
i.e the volume of one mole of gas at STP is 22.4 L
 The volume of the yellow box is
22.4 L. To its left is a basketball.
 5.3 Ideal Gas Law

1
Boyle’s law: V a (at constant n and T)
nT
P
Va
Charles’ law: V a T (at constant n and P) P
Avogadro’s law: V a n (at constant P and T)

nT nT
V = constant x =R
P P

PV  nRT
The molar gas constant, R, is the
constant of proportionality that relates
the molar volume of a gas to T/P.
Example: Determine the grams of O2 in a 50.0-L cylinder at
21°C when the O2 pressure is 15.7 atm.
Variable Value
P 15.7 atm
V 50.0 L
T (21 + 273) K = 294 K
n ?
PV
Solving the ideal gas law for n n=
RT
15.7 atm  50.0 L
n= = 32.5 mol
0.0821 L  atm/(K  mol)  294 K
Converting moles into mass of oxygen yields
32.0 g O 2
32.5 mol O 2  = 1.04  103 g O 2
1mol O 2
Q5-2; A small bubble rises from the bottom of a lake, where
the temperature and pressure are 8°C and 6.4 atm, to the
water’s surface, where the temperature is 25°C and the
pressure is 1.0 atm. Calculate the final volume (in mL) of
the bubble if its initial volume was 2.1 mL.
Ans: 14 ml

Q5-3 What is the volume (in liters) occupied by 49.8 g

of HCl (36.45g/mole) at STP?
Ans: 30.17 L
Prove the following statement: the pressure of a given amount of gas at a fixed volume is
proportional to the absolute temperature. This is sometimes called Amontons’ law.
 nR  P = constant  T
Using the ideal gas law: PV  nRT P =  T
V  PaT

Q; What volume in milliliters does a sample of nitrogen with a mass of 0.245 g

occupy at 21 °C and 750 torr?
Ans: 214 ml

Example: Sulfur hexafluoride (SF6) is a colorless and odorless gas. Calculate the pressure
(in atm) exerted by 1.82 moles of the gas in a steel vessel of volume 5.43 L at 69.5°C.
Ans: 9.42 atm

Example: Calculate the volume (in L) occupied by 7.40 g of NH3 at STP

Ans: 9.74L

Example: Argon is an inert gas used in light bulbs to retard the vaporization of the filament. A
certain light bulb containing argon at 1.20 atm and 18 0C is heated to 85 0C at constant
volume. What is the final pressure of argon in the light bulb (in atm)? Ans: 1.42 atm
 Gas Density: Molecular-weight Determination
 The density of a substance is its mass divided by its volume.
Hence, density is influenced by temperature and pressure.

 The ideal gas law can be used to calculate the density of a gas at
any temperature and pressure.

Q5-4: What is the density of oxygen, O2, in grams per liter at

25oC and 0.850 atm? Variable Value
P 0.850 atm
Ans: 1.11 g/l V 1 L (exact value)
T (25+273) K 298 K
n?

 Same calculation for Cl2; the density will be 2.46g/l

 Then the density of a gas is directly proportional to its Molecular
Weight

Q) Calculate the density of helium, He, in grams per liter at 21oC and 752 mmHg.
The density of air under these conditions is 1.188 g/L. What is the difference in mass
between 1 liter of air and 1 liter of helium? (This mass difference is equivalent to the
buoyant, or lifting, force of helium per liter.)
Example: Three 3.0-L flasks, each at a pressure of 878 mmHg,
are in a room. The flasks contain He (4 g/mole), Ar (20.2g/mol),
and Xe (131.23g/mole), respectively.
a. Which of the flasks contains the most atoms of gas?
b. Which of the flasks has the greatest density of gas?
c. If the He flask were heated and the Ar flask cooled, which of
the three flasks would be at the highest pressure?
d. Say the temperature of the He was lowered while that of the
Xe was raised. Which of the three flasks would have the
greatest number of moles of gas?
Assume the flasks are closed.
a. All flasks contain the same number of atoms (same volume).
b. The gas with the highest molar mass, Xe, has the greatest
density.
c. The flask at the highest temperature (the one containing He)
has the highest pressure.
d. The number of atoms is unchanged.
Density of gases

Density depends on MM of the gas; as MM increase the density increase; At

STP, 1mole O2: 32g/22.4= 1.43 g/l;1 mole CO2; 44g/22.4 = 1.96; He 0.179 g/l
 Gas Densities and Molar Mass
Density (d) Calculations
PM m is the mass of the gas in g
m
d=
V
=
RT
M is the molar mass of the gas
Molar Mass (M ) of a Gaseous Substance
dRT d is the density of the gas in g/L
M=
P
Example: a 200.0-mL flask at 99oC and a pressure of 733
mmHg is filled with the vapor of a volatile (easily vaporized)
liquid. The mass of the substance in the flask is 0.970 g. What
is the molecular mass of the liquid?

0.970g/0.00631mol =
154 g/mol; 154 amu
Q5-5: A gaseous compound of phosphorus and fluorine with
an empirical formula of PF2 (69g/mol) was found to have
a density of 5.60 g/L at 23.0 °C and 750. torr. Calculate its
molecular mass and its molecular formula.
•Know : Density; Temperature; Pressure
•Ans; MM= 138.9 g/m ; P2F4
Determining Molecular Mass of Gas

Example: A student allowed some of an inert gas to flow into a 300. mL gas bulb
until the pressure was 685 torr. The sample now weighed 1.45 g; its temperature
was 27.0 °C. What is the molecular mass of this gas? Which of the Group 7A gases
(inert gases) was it? Volume = 0.3 L; Temp= 300.2 K; P= 0.901 atm

n=
PV
=
( )(
0.901 atm 0.300 L ) = 0.01098 mole
RT ( –1
0.082057 atm L mol K –1
)(
300.2 K )
mass 1.45 g
Molar Mass = = = 132 g/mol
n 0.01098 mol

Gas = Xe (Atomic Mass = 131.29 g/mol)

Q) A 7.52 g sample of a gas with an empirical formula of NO2 occupies 2.00 L at a pressure
of 1.00 atm and 25 °C. Determine the molar mass and molecular formula of the
compound.
A. 45.0 g/mol, NO2
B. 90.0 g/mol, N2O4
C. 7.72 g/mol, NO
D. 0.0109 g/mol, N2O
E. Not enough data to determine molar mass
Stoichiometry and Gas Volumes
 Use the ideal gas law to find moles from a given volume, pressure, and
temperature, and vice versa.

• In reactions in which products and reactants are gases

– If T and P are constant
– Simple relationship among volumes
H2 + Cl2  2HCl
hydrogen + chlorine  hydrogen chloride
1 vol 1 vol 2 vol

Ex: Calculate the volume of ammonia formed by the

reaction of 25 L of hydrogen with excess nitrogen.
N2(g) + 3H2(g)  2NH3(g)

25 L H2 2 L NH3
´ = 17 L NH3
1 3 L H2
Q5-6: How many liters of N2(g) at 1.00 atm and 25.0 °C are
produced by the decomposition of 150. g of NaN3?
2NaN3(s)  2Na(s) + 3N2(g)
V=84.6 L

Q5-7: Air bags in automobiles can be inflated with

nitrogen using the rapid reaction of sodium azide, NaN3,
and iron (III) oxide, Fe2O3. How many grams of sodium
azide would be required to provide 75.0 L of nitrogen
gas at 25°C and 748 mmHg?
6NaN3 (s) + Fe2 O3 (s) 
 3Na 2 O(s) + 2Fe(s) + 9N2 (g)
Ans: 131g NaN3
Example: N2(g) + 3H2(g)  2NH3(g)
If 125 L H2 react with 50.0 L N2, what volume of NH3 can be expected?
H2 is limiting reagent 125 L H2 2 L NH3
´ = 83.3 L NH3
1 3 L H2

How many liters of SO3 will be produced when 25 L of sulfur dioxide reacts with 75 L of
oxygen? All gases are at STP. 2SO2 + O2 -----------> 2SO3
A. 25 L
Limiting Reactant?
B. 50 L
C. 100 L
D. 150 L
Dinitrogen pentoxide decomposes into oxygen gas and nitrogen dioxide. If all the gases are
at the same P and T, what volume of gas is produced when 13.0 L of dinitrogen pentoxide
gas completely decompose?
A. 13.0 L 2N2O5  4NO2 + O2
B. 32.5 L
C. 5.20 L So 5 L of gas (NO2 and O2) are produced for
D. 6.50 L every 2 L of N2O5 that decompose
E. 65.0 L

What volume in milliliters does a sample of nitrogen (28g/mol) with a mass of 0.245 g occupy
at 21 °C and 750 torr? Ans: 214 ml
Your Turn!
Dry ice is solid carbon dioxide. What is the pressure, in atm, of CO2 in a 50.0 L container at
35 °C when 33.0 g of dry ice becomes a gas?
A. 0.0432 atm
B. 0.0101 atm
C. 0.379 atm
D. 0.0800 atm
E. 37.9 atm

If 13.0 moles of N2O5 decompose into NO2 and O2 at 415 K in a 4.75 L container
that can’t expand or contract, after decomposition, how many times greater is the
pressure in the box than atmospheric pressure (approx. 1 atm)?
A. 13.0 times greater
P  233atm 2N2O5  4NO2 + O2
B. 32.5 times greater
C. 466 times greater Pgas 233 atm
D. 93.2 times greater   233 times greater
Patm 1.00 atm
E. 233 times greater

Q) How many liters of chlorine gas, Cl2, can be obtained at 40oC and 787 mmHg from
9.41 g of hydrogen chloride, HCl, according to the following equation?

2KMnO4(s) + 16HCl(aq) -------- 8H2O(l) + 2KCl(aq) + 2MnCl2(aq) + 5Cl2(g)

Example: In one lab, the gas collecting apparatus used a gas bulb with a volume of 250.
mL. How many grams of Na2CO3(s) (106 g/mol) would be needed to prepare enough
CO2(g) to fill this bulb when the pressure is at 738 torr and the temperature is 23 °C?
Na2CO3(s) + 2 HCl(aq)  2 NaCl(aq) + CO2(g) + H2O

PV 0.971 atm ´ 0.250 L

n= = = 9.989 × 10–3 mole CO2
RT 0.082057 atm L mol–1 K –1 ´ 296.2 K

i.e: 9.989 × 10–3 mole Na2CO3 ; Then 9.989 × 10–3 mole x 106 g/mole = 1.06 g

2Na(s) + 2H2O(l ) → 2NaOH(aq) + H2(g)

How many grams of sodium (23g/mol) are required to produce 20.0 L of hydrogen gas
at 25.0 °C, and 750. torr?
A. 18.6 B. 57.0 g C. 61.3 g D. 9.62 g E. 37.1 g
Solid sodium carbonate, when heated, decomposes to form sodium oxide and carbon
dioxide. If 27.5 g of sodium carbonate is decomposed at 925 oC and the gas that results
is collected in a 25.0 L container (assume Tgas = 925 oC), would you worry about the
container bursting?
A. yes, high T will cause high P
B. yes, P will be 102 atm (very high!)
C. no, P will only be 1.02 atm
D. no, P will only be 0.788 atm
 5.5 Gas Mixtures: Law of Partial
 Dalton found that in a mixture of unreactive gases, each gas
behaves as if it were the only gas in the mixture as far as pressure is
concerned.

Originally (left), flask A contains He at 152 mmHg and flask B contains O2 at

608 mmHg. Flask A is then filled with oil forcing the He into flask B (right). The
new pressure in flask B is 760 mmHg.
Partial Pressure
The pressure exerted by a particular gas in a mixture.
Dalton’s Law of Partial Pressures
The sum of the partial pressures of all the different gases in a
mixture is equal to the total pressure of the mixture:
P = PA + PB + PC + . . .

Ptotal = Pa + Pb + Pc + × × ×
naRT nbRT ncRT
= + + +×××
V V V
æ RT ö
• Rearranging (
Ptotal = na + nb + nc + × × × çç
èV
) ÷÷
ø
æ RT ö
• Or Ptotal = ntotal çç ÷÷
èV ø
• Where ntotal = na + nb + nc + ···
ntotal = sum of number moles of various gases in mixture
Example: Partial Pressure
Mixtures of helium and oxygen are used in scuba diving tanks to help prevent “the
bends.” For a particular dive, 46 L He at 25 °C and 1.0 atm and 12 L O2 at 25 °C
and 1.0 atm were pumped into a tank with a volume of 5.0 L. Calculate the partial
pressure of each gas and the total pressure in the tank at 25 °C.
Pi Vi 1.0 atm  46 L Pi Vi 1.0 atm  12 L
PHe    9.2 atm PO2    2.4 atm
Vf 5.0 L Vf 5.0 L
Ptotal = PHe + PO = 9.2 atm + 2.4 atm = 11.6 atm
2

A mixture of 250 mL of methane, CH4, at 35 ˚C and 0.55 atm and 750 mL of

propane, C3H8, at 35˚ C and 1.5 atm, were introduced into a
10.0 L container. What is the final pressure, in torr, of the mixture?

A. 95.6 torr PCH =

(0.55 atm) (0.250 L) = 0.0138 atm
B. 6.20 × 104 torr
4
10.0 L

C. 3.4 × 103 torr PC H =

( )(
1.5 atm 0.750 L ) = 0.112 atm
3 8
10.0 L
D. 760 torr æ 760 torr ö
E. 60 torr (
PT = 0.0138 atm + 0.112 atm çç
è atm ø
) ÷÷ = 95.6 torr
Mole Fraction
The mole fraction of a component gas is the fraction of moles of
that component in the total moles of gas mixture.
nA nA
cA = =
n A + nB + nC + × × × + nZ n total
Mole % = c A ´ 100%

æV ö
If V and T are constant ; For mixture of gases in one
n A = PA çç ÷÷ container
è RT ø

PA nA
cA = = PA = c A ´ Ptotal
Ptotal n total
A mixture consists of 122 moles of N2, 137 moles of C3H8, and 212 moles of CO2. What is the
mole fraction of each?
A. 0.259 N2, 0.291 C3H8, 0.450 CO2
B. 0.803 N2, 0.206 C3H8, 0.320 CO2
C. 0.122 N2, 0.137 C3H8, 0.212 CO2
D. 3.86 N2, 3.44 C3H8, 2.22 CO2
E. 1.75 N2, 1.46 C3H8, 4.53 CO2

Example: The partial pressure of oxygen was observed to be 156 torr in air
with a total atmospheric pressure of 743 torr. Calculate the mole fraction of
O2 present
PA 156 torr
cA = c O2 = = 0.210
Ptotal 743 torr

Example: The mole fraction of nitrogen in the air is 0.7808. Calculate the partial
pressure of N2 in air when the atmospheric pressure is 760. torr.
PN =cN ´ Ptotal
2 2

PN = 0.7808 ´ 760 torr = 593 torr

2
Example: A 1.00-L sample of dry air at 25°C and 786 mmHg
contains 0.925 g N2, plus other gases including oxygen, argon,
and carbon dioxide.
Determine the partial pressure (in mmHg) of N2 in the air sample
Determine the mole fraction and mole percent of N2 in the mixture.
1 mol N 2
0.925 g N 2  = 0.330 mol N 2
28.0 g N 2
nN2 RT
PN2 =
V
0.0330 mol  0.0821 L  atm/(K  mol)  298 K
=
1.00 L
= 0.807 atm (= 613 mmHg)

PN 2 613 mmHg
Mole fraction of N 2 = = 0.780 = 78.0%
P 786 mmHg
Q5-8: A 10.0-L flask contains 1.031 g O2 (32.00 g/mol) and 0.572
g CO2 (44.01 g/mol) at 18oC. What are the partial pressures of
oxygen and carbon dioxide? What is the total pressure? Ans: 0.108
What is the mole fraction of oxygen in the mixture? Ans: 0.712

Example: A flask equipped with a valve contains 3.0 mol of H2 gas. You introduce 3.0 mol of Ar
gas into the flask via the valve and then seal the flask.
a. What happens to the pressure of just the H2 gas in the flask after the introduction of the Ar?
If it changes, by what factor does it do so?
b. How do the pressures of the Ar and the H2 in the flask compare?
c. How does the total pressure in the flask relate to the pressures of the two gases?
a. Nothing happens to the pressure of H2.
b. The pressures are equal because the moles are equal.
c. The total pressure is the sum of the pressures of the two gases.
Your Turn!
A mixture of 250 mL of methane, CH4, at 35˚ C and 0.55 atm and 750 mL of propane,
C3H8, at 35˚ C and 1.5 atm was introduced into a 10.0 L container. What is the mole
fraction of methane in the mixture?
0.55 atm ´ 0.250 L
A. 0.50 PCH
4
= = 0.0138 atm
10.0 L
B. 0.11
1.5 atm ´ 0.750 L
C. 0.89 PC H
3 8
= = 0.112 atm
10.0 L
D. 0.25 0.0138 atm
E. 0.33 c CH4
= = 0.110
0.0138 atm + 0.112 atm

A mixture consists of 122 moles of N2, 137 moles of C3H8, and 212 moles of CO2 at 200 K in a 75.0
L container. What is the total pressure of the gas and the partial pressure of CO2?
A. 46.4 atm, 20.9 atm
B. 103 atm, 26.7 atm   
471 moles 0.0821L atm mol-1 K -1 200 K  P
total  103 atm
C. 103 atm, 46.4 atm Ptotal  75.0 L
D. 103 atm, 29.9 atm
E. 46.4 atm, 46.4 atm 212 moles CO 2
mole fraction CO 2 :  0.450
122  137  212 total

 
PCO2   CO2 Ptotal   0.450 103 atm  PCO2  46.4 atm
43
Collecting Gas Over Water
 Gases are often collected over water. The result is a mixture of
the gas and water vapor.
 The partial pressure of water depends only on temperature.
Collecting Gas Over Water
• Application of Dalton’s Law of Partial Pressures
• Gases that don’t react with water can be trapped over water
• Gas in bottle is mixture of water vapor and gas being collected
 Gas saturated with water vapor
= “Wet” gas

When wet gas collected over water,

we usually want to know how much
“dry” gas this corresponds to
Ptotal = Pgas + Pwater
Rearranging
Pgas = Ptotal – Pwater
Example: Hydrogen gas is produced by the reaction of HCl on
zinc metal.
2HCl ( aq) + Zn(s) 
 ZnCl2 (aq) + H2 (g )
The gas is collected over water. Determine the mass of hydrogen
collected if 156 mL of gas is collected at 19°C and 769 mmHg
total pressure. The pressure of the water vapor at 19°C is
16.5 mmHg.
P = PH 2 + PH2 O
PH2 = P – PH2O = (769 – 16.5) mmHg = 752 mmHg
1 atm
752 mmHg  = 0.989 atm
760 mmHg
PV 0.989 atm  0.156 L
n=  = 0.00641 mol
RT 0.0821 L  atm/(K  mol)  293 K

2.02 g H 2
0.00664 mol H 2  = 0.0130 g H 2
1 mol H 2
Q5-8: A sample of oxygen is collected over water at 20.0 ˚C and
a pressure of 738 torr. Its volume is 310 mL. The vapor pressure
of water at 20 ˚C is 17.54 torr.
a. What is the partial pressure of O2? Ans: 720 torr
b. What would the volume of O2 be when dry at STP?
Ans: V2 = 274 mL; then when water vapor is removed from the gas, the dry
oxygen will occuby a volum of 286 ml at STP

Q) Oxygen can be prepared by heating potassium chlorate, KClO3, with manganese

dioxide as a catalyst. The reaction is

How many moles of O2 would be obtained from 1.300 g KClO3? Ans: 0.015 mole of O2
If this amount of O2 were collected over water at 23oC and at a total pressure of 745
mmHg, what volume would it occupy? The vapor pressure of water at 23 ˚C is 21.1 torr.
Ans: PO2 = 723.9 mmHg= 0.95atm; v=nRT/P = 0.384 L

Q) Oxygen gas generated in the thermal decomposition of potassium chlorate is collected over
water. At 24 oC and an atmospheric pressure of 762 mm Hg, the volume of gas collected is 0.128
L. The vapor pressure of water is 22.4 torr. What mass of oxygen is created?
Ans: nO2= = 5.09 x 10-3 mol; 0.163g
 5.6 Kinetic Theory of Ideal Gas
A theory, developed by physicists, that is based on
the assumption that a gas consists of molecules
in constant random motion.

Kinetic energy is related to the mass and velocity:

1
EK  m( speed )2 m = mass
2
Kinetic Theory of Ideal Gas: Kinetic-theory
model of gas
Postulate 1: Gases are composed of molecules whose pressure
size is negligible compared with the average distance According to kinetic
theory, gas pressure
between them. Most of the volume occupied by a
is the result of the
gas is empty space. bombardment of the
container walls by
Postulate 2: Molecules move randomly in straight lines constantly moving
in all directions and at various speeds. This means that molecules.
properties of a gas that depend on the motion of
molecules, such as pressure, will be the same in all
directions.
Postulates of the Kinetic Theory

Postulate 3: The forces of attraction or repulsion between two molecules

in a gas are very weak or negligible, except when they collide. This means
that a molecule will continue moving in a straight line with undiminished speed
until it collides with another gas molecule or with the walls of the container.

Postulate 4: When molecules collide with one another, the collisions are
elastic. In an elastic collision, the total kinetic energy remains constant; no
kinetic energy is lost. To understand the difference between an elastic and an
inelastic collision, compare the collision of two hard steel spheres

Postulate 5: The average

kinetic energy of a molecule is
proportional to the absolute
temperature: the higher the
temperature, the greater the
molecular kinetic energy.
An elastic collision is one in which no kinetic energy is
lost. The collision on the left causes the ball on the right
to swing the same height as the ball on the left had
initially, with essentially no loss of kinetic energy.
 (A) A container where the gas molecules are at
Molecular description of Avogadro’s law atmospheric pressure (Pinside = Patm). The
pressure is due to the force and frequency of
molecular collisions with the container walls.
(B) The container after increasing the number of
gas molecules while not allowing the piston to
move; the frequency of collisions of the gas
molecules with the walls of the container has
increased, then (Pinside > Patm).
(C) Container after the molecules are allowed to
move the piston and increase the volume.
The concentration of gas molecules and
frequency of collisions with the container walls
have decreased,\; (Pinside = Patm).
Molecular
description of (A) A fixed number of moles of gas in a container at room
Boyle’s law temperature. The pressure in the container is due to the
force and frequency of molecular collisions with the
container walls.
(B) The same number of moles of gas at the same
temperature as A, but in a container of greater volume.
Because of the larger container volume, the gas
concentration is now lower, which leads to a decrease
in the frequency of molecular collisions per unit of
wall area, resulting in a lower pressure.
 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, i.e., it depends on momentum, mu.
 The frequency of collisions is proportional to the average speed, u, and the
number of molecules, N, and is inversely proportional to the volume, V.

 1 
P a  u × × N  × mu Then PV  Nmu 2
 V 

 The average kinetic energy of a molecule of mass m and average speed u is

1/ mu2.
2
 Thus PV is proportional to the average kinetic energy of the molecule.

 However, the average kinetic energy is also proportional to the absolute

temperature. Therefore,
PV  nT

PV  nRT
 5.7 Molecular Speeds; Diffusion and Effusion
 According to kinetic theory, molecular speeds vary over a wide
range of values. This distribution depends on temperature, so it
increases as the temperature increases.
Root-mean Square (rms) Molecular Speed, u
 A type of average molecular speed, equal to the speed of a
molecule that has the average molecular kinetic energy
1
3RT  3RT  2
u   
Mm  Mm 
 where R is the molar gas constant, T is the absolute temperature, and Mm
is the molar mass for the gas.
 If SI units are used for R (= 8.31 kg·m2/s2·K·mol), T(K) and Mm
(kg/mol), rms speed will be in meters per second.
 Joule is kg·m2/s2
  Maxwell predicted the
distributions of molecular
speeds at various
temperatures. The graph
shows rms (m/s) for H2 at
0°C and 500°C.

Example; Calculate the rms speed of

O2 molecules in a cylinder at 21oC
and 15.7 atm.
o Temp: (21 + 273) K = 294 K.
o Molar Mass of O2 = 32.0 x 10-3 kg/mol
o R = 8.31 kgm2/(s2.K.mol).

Ex: At what temperature in K would O3 (48.00 g/mole) molecules have a root mean
square speed (rms) equal to that of O2 (32.00 g/mole) molecules at 245K? R = 8.31
kgm2/(s2.K.mol) Ans: 419 K
Diffusion and Effusion
 Diffusion is the process whereby a gas spreads out through
another gas to occupy the space uniformly.
Left: Concentrated aqueous ammonia in the beaker
releases ammonia gas into the glass tube, which
contains a strip of wet indicator paper. In the
molecular view there are only nitrogen and oxygen
molecules (air) surrounding the indicator paper.
Right: The indicator changes color as the ammonia
gas diffuses upward through the air
in the tube. The molecular view depicts the
appearance of the NH3 molecules in the tube due to
diffusion.

e.g., Perfume in room (if

convective forces are absent)
Effusion is the process by which a gas flows through a small hole
in a container. A pinprick in a balloon is one example of effusion.

 Movement of gas molecules through

extremely small opening into vacuum

Graham’s Law of Effusion

The rate of effusion of gas
molecules through a particular Rate of effusion of molecules  1
hole is inversely proportional Mm
to the square root of the
molecular mass of the gas.
Example: Calculate the ratio of effusion rates of molecules and
CO2 and SO2 from the same container and at the same
temperature and pressure. 1
Rate of effusion of CO22 M m (CO 2 )
=
Rate of effusion of SO 2 1
M m (SO 2 )
M m (SO 2 )
=
M m (CO 2 )
64.1 g/mol
=
44.0 g/mol
= 1.21
 CO2 diffuses1.21 times faster than sulfur dioxide
 Note: Consider the experimental
apparatus shown. In this setup,
each round flask contains a
gas, and the long tube contains
no gas (that is, it is a vacuum).

a. We use 1.0 mol of He for

experiment X and 1.0
mol of Ar for experiment Y. If both valves are opened at the same time, which gas
would you expect to reach the end of the long tube first? Ans: He has small MM
and it will reach first
b. If you wanted the Ar to reach the end of the long tube at the same time as the He,
what experimental condition (that is, you cannot change the equipment) could you
change to make this happen? Ans: Increase the temp of Ar or Open the valves
at two different times, allowing Ar more time by a factor equal to the square root of
the ratio of molar masses of Ar to He, or approximately 3.16 times longer.

Example: Calculate the ratio of the effusion rates of hydrogen gas (H2; 2.016 g/mol)
and uranium hexafluoride (UF6; 352.016 g/mol) - a gas used in the enrichment
process to produce fuel for nuclear reactors. Ans: about 13 times more
Your Turn!
If it takes methane (CH4; 16.04 g/mol) 3.0 minutes to diffuse 10.0 m, how long will it
take sulfur dioxide (SO2; 64.06 g/mol) to travel the same distance?
A. 1.5 min
B. 12.0 min
C. 1.3 min
D. 0.75 min
E. 6.0 min

How many times faster does 235UF6 (MW = 349.0 g/mol) effuse compared to 238UF6
(MW = 352.0 g/mol)?
A. 0.9957
B. 1.004
C. 0.994
D. 1.009
E. 0.9911