Chapter 4

STATE OF MATTER

1
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 Topic
CHAPTER 4
4.1 Introduction
4.2 Gas Laws
4.3 Ideal Gas Equation
4.4 Mixtures of Gases & Dalton’s Law of Partial
Pressures
4.5 Kinetic Molecular Theory of Gasses
4.6 Graham’s Law of Diffusion and Effusion
4.7 Real Gases: Deviations from Ideal Behavior
4.8 Colligative Properties
4.9 Phase Diagram
Elements that exist as gases at 250C and 1 atmosphere

3
4
 An Overview of the Physical States of Matter
Distinguishing gases from liquids and solids

•Gas volume changes significantly with pressure.

– Solid and liquid volumes are not greatly affected by
pressure.
•Gas volume changes significantly with temperature.
– Gases expand when heated and shrink when cooled.
– The volume change is 50 to 100 times greater for gases
than for liquids and solids.
•Gases flow very freely.
•Gases have relatively low densities.
•Gases form a solution in any proportions.
– Gases are freely miscible with each other.
• Gas molecules are constantly in motion
• As they move and strike a surface, they
push on that surface
 push = force
• If we could measure the total amount of
force exerted by gas molecules hitting the
entire surface at any one instant, we would
know the pressure the gas is exerting

Pressure = Force
Area
(force = mass x acceleration)
Units of Pressure
1 pascal (Pa) = 1 N/m2
1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa 6
The pressure outside a jet plane flying at high altitude falls
considerably below standard atmospheric pressure. Therefore,
the air inside the cabin must be pressurized to protect the
passengers.
What is the pressure in atmospheres in the cabin if the
barometer reading is 688 mmHg?

Strategy Because 1 atm = 760 mmHg, the following

conversion factor is needed to obtain the pressure in
atmospheres
Solution The pressure in the cabin is given by
The atmospheric pressure in San Francisco on a certain day was 732
mmHg.
What was the pressure in kPa?
Strategy
Here we are asked to convert mmHg to kPa.
1 atm = 1.01325 × 105 Pa = 760 mmHg
Solution The pressure in kPa is
 Properties and Measurements of Gases
The Pressure of a Gas
• Gas pressure is a result of the constant
movement of the gas molecules and their
collisions with the surfaces around them
• The pressure of a gas depends on several
factors
 number of gas particles in a given
volume
 volume of the container
 average speed of the gas particles
Measurements of Gases
Pressure of gas can be measure using:
• Barometer
• Manometers
• We measure air pressure
with a barometer
• Column of mercury supported
by air pressure
• Force of the air on the
surface of the mercury
counter balances the force of
gravity on the column of
mercury
Manometers Used to Measure Gas Pressures
closed-tube open-tube

11
 Open-end manometer

When Pgas is less than Patm, When Pgas is greater than Patm,
subtract Dh from Patm. add Dh to Patm.
Pgas < Patm Pgas > Patm
Pgas = Patm - Dh Pgas = Patm + Dh
 Closed-end manometer

The Hg levels are equal A gas in the flask pushes the Hg

because both arms of the U level down in the left arm.
tube are evacuated.
The difference in levels, Dh, equals
the gas pressure, Pgas.
 Ideal Gas Equation
Boyle’s law: P a 1 (at constant n and T)
V
Charles’s law: V a T (at constant n and P)
Avogadro’s law: V a n (at constant P and T)

nT
Va
P
nT nT
V = constant x =R R is the gas constant
P P

PV = nRT

15
The Gas Laws
The gas laws describe the physical behavior of gases in terms
of 4 variables:
– pressure (P)
– temperature (T)
– volume (V)
– amount (number of moles, n)
An ideal gas is a gas that exhibits linear relationships among
these variables.
No ideal gas actually exists, but most simple gases behave
nearly ideally at ordinary temperatures and pressures.
 Boyle’s Law

At constant temperature, the volume occupied by a

fixed amount of gas is inversely proportional to the
external pressure.

V 1 or PV = constant
P

At fixed T and n,
P decreases as V increases
P increases as V decreases
 P a 1/V At constant temperature, the volume occupied by a
fixed amount of gas is inversely proportional to the
P x V = constant external pressure.
P1 x V1 = P2 x V2
18
Boyle’s Experiment, The Relationship Between The
Volume and Pressure of a Gas.
Boyle’s Experiment, The Relationship Between The
Volume and Pressure of a Gas.
 Sample Problem Applying the Volume-Pressure Relationship
4.2.1
PROBLEM: Boyle’s apprentice finds that the air trapped in a J tube
occupies 24.8 cm3 at 1.12 atm. By adding mercury to the
tube, he increases the pressure on the trapped air to 2.64
atm. Assuming constant temperature, what is the new
volume of air (in L)?

PLAN: The temperature and amount of gas are fixed, so this

problem involves a change in pressure and volume only.

V1 (cm3)
unit conversions

V1 (L)
multiply by P1/P2

V2 (L)
Sample Problem
4.2.1
SOLUTION:

P1 = 1.12 atm P2 = 2.64 atm

V1 = 24.8 cm3 V2 = unknown n and T are constant

24.8 cm3 x 1 mL x L
= 0.0248 L
1 cm3 103 mL

P1V1 P2V2
= P1V1 = P2V2
n1T1 n2T2

V2 = V1 x P1 = 0.0248 L x 1.12 atm = 0.0105 L

P2 2.46 atm
 Boyle’s Law: A Molecular View

• Pressure is caused by the molecules striking the sides of

the container
• When you decrease the volume of the container with the
same number of molecules in the container, more
molecules will hit the wall at the same instant
• This results in increasing the pressure
 Summary of Gas Laws
Boyle’s Law

24
 Charles’s Law

At constant pressure, the volume occupied by a

fixed amount of gas is directly proportional to its
absolute (Kelvin) temperature.
V
VT = constant
T

At fixed T and n,
P decreases as V increases
P increases as V decreases
 Variation of Gas Volume with Temperature
at Constant Pressure
Charles’s & Gay-Lussac’s Law
• If you plot volume vs.
temperature for any gas at
constant pressure, the points
will all fall on a straight line
• If the lines are extrapolated
back to a volume of “0,” they
all show the same
temperature, −273.15 °C,
called absolute zero

VαT
V = constant x T Temperature must be
in Kelvin
V1/T1 = V2 /T2 T (K) = t (0C) + 273.15 26
 Charles’s Law – A Molecular View

• The pressure of gas inside

and outside the balloon are
the same
• At high temperatures, the gas
molecules are moving faster,
so they hit the sides of the
balloon harder – causing the
volume to become larger
• At low temperatures, the gas
molecules are not moving as
fast, so they don’t hit the sides
of the balloon as hard –
therefore the volume is small
Charles’s Law

28
 Gay-Lussac’s Law

Pressure directly proportional to kelvin

temperature

P ̰∝ T (V and Mass constant)

P = constant
T
 Sample Problem Applying the Pressure-Temperature
4.2.2 Relationship

PROBLEM: A steel tank used for fuel delivery is fitted with a safety
valve that opens when the internal pressure exceeds
1.00x103 torr. It is filled with methane at 23°C and 0.991
atm and placed in boiling water at exactly 100°C. Will the
safety valve open?
PLAN: We must determine if the pressure will exceed 1.00x103 torr
at the new temperature. Since the gas is in a steel tank, the
volume remains constant.

P1 (atm) T1 and T2 (°C)

1 atm = 760 torr K = °C + 273.15

P1 (torr) T1 and T2 (K)

multiply by T2/T1

P2 (torr)
Sample Problem
4.2.2
SOLUTION:
P1 = 0.991 atm P2 = unknown
T1 = 23°C T2 = 100.°C n and V are constant

0.991 atm x 760 torr = 753 torr T1 = 23 + 273.15 = 296 K

1 atm T2 = 100. + 273.15 = 373 K

P1V1 P2V2 P1 P2
= =
n1T1 n2T2 T1 T2

P2 = P1 x T2 = 753 torr x 373 K = 949 torr

T1 296 K

The safety valve will not open, since P2

is less than 1.00 x 103 torr.
 Combined Gas Law

Combining Boyle’s Law, Charles’ Law and Gay-Lussac’s Law gives:

PV = constant (mass constant)

T
Application form: P1 V1 = P2 V2
T1 T2
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.
Strategy In solving this kind of problem, where a lot of
information is given, it is sometimes helpful to make a sketch of
the situation, as shown here:

What temperature unit should be used in the calculation?

Solution

We assume that the amount of air in the bubble remains

constant, that is, n1 = n2 so that
The given information is summarized:

Initial Conditions Final Conditions

P1 = 6.4 atm P2 = 1.0 atm
V1 = 2.1 mL V2 = ?
T1 = (8 + 273) K = 281 K T2 = (25 + 273) K = 298 K

Rearranging Equation (5.10) gives

 Avogadro’s Law
Amedeo Avogadro (1776–1856)

• Volume directly proportional to the number of gas molecules

V = constant x n
constant P and T
more gas molecules = larger volume
• Count number of gas molecules by moles
• Equal volumes of gases contain equal numbers of
molecules
the gas doesn’t matter
 Avogadro’s Law
Constant temperature
V a number of moles (n) Constant pressure

V = constant x n

V1 / n1 = V2 / n2

38
Avogadro’s Law
 Sample Problem
Applying the Volume-Amount Relationship
4.2.4
PROBLEM: A scale model of a blimp rises when it is filled with helium to
a volume of 55.0 dm3. When 1.10 mol of He is added to the
blimp, the volume is 26.2 dm3. How many more grams of He
must be added to make it rise? Assume constant T and P.

PLAN: The initial amount of helium (n1) is given, as well as the initial
volume (V1) and the volume needed to make it rise (V2). We
need to calculate n2 and hence the mass of He to be added.

n1 (mol) of He
multiply by V2 /V1
n2 (mol) of He
subtract n1
mol to be added
multiply by M
g to be added
Sample Problem 4.2

SOLUTION:
n1 = 1.10 mol n2 = unknown
V1 = 26.2 dm3 V2 = 55.0 dm3 T and P are constant

P1V1 P2V2 V1 V2
= =
n1 T 1 n2T2 n1 n2

n2 = n 1 x V2 3
= 1.10 mol x 55.0 dm = 2.31 mol He
V1 26.2 dm3

Additional amount of He needed = 2.31 mol – 1.10 mol = 1.21 mol He

4.003 g He
1.21 mol He x = 4.84 g He
1 mol He
Avogadro’s Law

42
 Ideal Gas Equation
Boyle’s law: P a 1(at constant n and T)
V
Charles’s law: V a T (at constant n and P)
Avogadro’s law: V a n (at constant P and T)

nT
Va
P
nT nT
V = constant x =R R is the gas constant
P P

PV = nRT

43
Gas Behavior at Standard Conditions

STP or standard temperature and pressure

specifies a pressure of 1 atm (760 torr) and a
temperature of 0°C ( 273.15 K).

The standard molar volume is the volume of 1 mol

of an ideal gas at STP.
Standard molar volume = 22.4141 L or 22.4 L
Standard molar volume.
The conditions 0 0C and 1 atm are called standard
temperature and pressure (STP).

Experiments show that at STP, 1 mole of an ideal gas

occupies 22.414 L.

PV = nRT
PV (1 atm)(22.414L)
R= =
nT (1 mol)(273.15 K)

R = 0.082057 L • atm / (mol • K)

46
Sulfur hexafluoride (SF6) is a
colorless and odorless gas.

Due to its lack of chemical

reactivity, it is used as an
insulator in electronic
equipment.

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.
Strategy
The problem gives the amount of the gas and its volume and
temperature.

Is the gas undergoing a change in any of its properties?

What equation should we use to solve for the pressure?

What temperature unit should we use?

Solution Because no changes in gas properties occur, we can
use the ideal gas equation to calculate the pressure.

Rearranging ideal gas law equation, we write

Calculate the volume (in L) occupied by 7.40 g of NH3 at STP.
Strategy
What is the volume of one mole of an ideal gas at STP?

How many moles are there in 7.40 g of NH3?

Solution
Recognizing that 1 mole of an ideal gas occupies 22.41 L at
STP and using the molar mass of NH3 (17.03 g), we write the
sequence of conversions as
So the volume of NH3 is given by

It is often true in chemistry, particularly in gas-law calculations,

that a problem can be solved in more than one way. Here the
problem can also be solved by first converting 7.40 g of NH3 to
number of moles of NH3, and then applying the ideal gas
equation (V = nRT/P). Try it.

Check Because 7.40 g of NH3 is smaller than its molar mass,

its volume at STP should be smaller than 22.41 L. Therefore,
the answer is reasonable.
 Density at Standard Conditions

• Density is the ratio of mass to volume

• Density of a gas is generally given in g/L
• The mass of 1 mole = molar mass
• The volume of 1 mole at STP = 22.4 L
 Gas Density

• Density is directly proportional to molar mass

Density (d) Calculations

m PM m is the mass of the gas in g

d= =
V RT M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT
M= d is the density of the gas in g/L
P

55
Calculate the density of carbon dioxide (CO2) in grams per liter
(g/L) at 0.990 atm and 55°C.
Strategy We need Equation (5.11) to calculate gas density.

Is sufficient information provided in the problem?

What temperature unit should be used?

Solution To use Equation (5.11), we convert temperature to

kelvins (T = 273 + 55 = 328 K) and use 44.01 g for the molar
mass of CO2:
Alternatively, we can solve for the density by writing

Assuming that we have 1 mole of CO2, the mass is 44.01 g.

The volume of the gas can be obtained from the ideal gas
equation
Therefore, the density of CO2 is given by

Comment ln units of grams per milliliter, the gas density is

1.62 × 10−3 g/mL, which is a very small number. In comparison,
the density of water is 1.0 g/mL and that of gold is 19.3 g/cm3.
A chemist has synthesized a greenish-yellow gaseous
compound of chlorine and oxygen and finds that its density is
7.71 g/L at 36°C and 2.88 atm.

Calculate the molar mass of the compound and determine its

molecular formula.
Strategy
we can calculate the molar mass of a gas if we know its density,
temperature, and pressure.The molecular formula of the
compound must be consistent with its molar mass. What
temperature unit should we use?
Solution From Equation

Alternatively, we can solve for the molar mass by writing

From the given density we know there are 7.71 g of the

gas in 1 L.
The number of moles of the gas in this volume can be obtained
from the ideal gas equation

Therefore, the molar mass is given by

Gas Stoichiometry

64
Calculate the volume of O2 (in liters)
required for the complete combustion
of 7.64 L of acetylene (C2H2)
measured at the same temperature
and pressure.

The reaction of calcium carbide (CaC2)

with water produces acetylene (C2H2), a
flammable gas.
Strategy Note that the temperature and pressure of O2 and
C2H2 are the same. Which gas law do we need to relate the
volume of the gases to the moles of gases?

Solution According to Avogadro’s law, at the same

temperature and pressure, the number of moles of gases are
directly related to their volumes. From the equation, we
have 5 mol O2 ≏ 2 mol C2H2; therefore, we can also write
5 L O2 ≏ 2 L C2H2. The volume of O2 that will react with 7.64 L
C2H2 is given by
Sodium azide (NaN3) is used in some
automobile air bags. The impact of a
collision triggers the decomposition of
NaN3 as follows:

The nitrogen gas produced quickly

inflates the bag between the driver
and the windshield and dashboard.

Calculate the volume of N2 generated

at 80°C and 823 mmHg by the An air bag can protect the
decomposition of 60.0 g of NaN3. driver in an automobile
collision.
Strategy From the balanced equation we see that
2 mol NaN3 ≏ 3 mol N2 so the conversion factor between NaN3
and N2 is

Because the mass of NaN3 is given, we can calculate the

number of moles of NaN3 and hence the number of moles of N2
produced.

Finally, we can calculate the volume of N2 using the ideal gas

equation.
Solution First we calculate number of moles of N2 produced by
60.0 g NaN3 using the following sequence of conversions

so that

The volume of 1.38 moles of N2 can be obtained by using the

ideal gas equation:
Aqueous lithium hydroxide solution is used to purify air in
spacecrafts and submarines because it absorbs carbon dioxide,
which is an end product of metabolism, according to the
equation

The pressure of carbon dioxide inside the cabin of a submarine

having a volume of 2.4 × 105 L is 7.9 × 10−3 atm at 312 K. A
solution of lithium hydroxide (LiOH) of negligible volume is
introduced into the cabin. Eventually the pressure of CO2 falls
to 1.2 × 10−4 atm. How many grams of lithium carbonate are
formed by this process?
Strategy How do we calculate the number of moles of CO2
reacted from the drop in CO2 pressure?

From the ideal gas equation we write

At constant T and V, the change in pressure of CO2, DP,

corresponds to the change in the number of moles of CO2, Dn.
Thus,

What is the conversion factor between CO2 and Li2CO3?

Solution The drop in CO2 pressure is
(7.9 × 10−3 atm) − (1.2 × 10−4 atm) or 7.8 × 10−3 atm
Therefore, the number of moles of CO2 reacted is given by

From the chemical equation we see that

1 mol CO2 1 mol Li2CO3

≏
so the amount of Li2CO3 formed is also 73 moles.
Then, with the molar mass of Li2CO3 (73.89 g), we calculate its
mass:
 Dalton’s Law
The total P of a mixture of gases is just the
sum of the pressure that each gas would
exert if it were present alone.

Pi = Xi PT Pi= Partial pressure

-The pressure of individual gas
components in the mixture.

Xi=Mole Fraction
-A dimensionless quantity
that expresses the ratio of the
number of moles of one
component to the number of all
components present.
Dalton’s Law of Partial Pressures
V and T are constant

P1 P2 Ptotal = P1 + P2
75
Consider a case in which two gases, A and B, are
in a container of volume V.
nART nA is the number of moles of A
PA =
V
nBRT nB is the number of moles of B
PB =
V
nA nB
PT = PA + PB XA = XB =
nA + n B nA + nB

PA = XA PT PB = XB PT

mole fraction (Xi ) = ni

Pi = Xi PT nT

76
A mixture of gases contains 4.46 moles of neon (Ne), 0.74 mole
of argon (Ar), and 2.15 moles of xenon (Xe).

Calculate the partial pressures of the gases if the total pressure

is 2.00 atm at a certain temperature.
Strategy What is the relationship between the partial pressure
of a gas and the total gas pressure?

How do we calculate the mole fraction of a gas?

Solution According to Equation (5.14), the partial pressure of

Ne (PNe) is equal to the product of its mole fraction (XNe) and
the total pressure (PT)
Using Equation (5.13), we calculate the mole fraction of Ne as
follows:

Therefore,
Similarly,

and

Check Make sure that the sum of the partial pressures is equal
to the given total pressure; that is,

(1.21 + 0.20 + 0.586) atm = 2.00 atm.

 Collecting a Gas over Water

2KClO3 (s) 2KCl (s) + 3O2 (g) PT = PO2 + PH2 O

81
Vapor of Water and Temperature

82
Oxygen gas generated by the decomposition of potassium
chlorate is collected as shown in Figure

The volume of oxygen collected at 24°C and atmospheric

pressure of 762 mmHg is 128 mL.

Calculate the mass (in grams) of oxygen gas obtained.

The pressure of the water vapor at 24°C is 22.4 mmHg.

Strategy To solve for the mass of O2 generated, we must first
calculate the partial pressure of O2 in the mixture.

What gas law do we need?

How do we convert pressure of O2 gas to mass of O2 in grams?

Solution From Dalton’s law of partial pressures we know that

Therefore,

From the ideal gas equation we write

where m and are the mass of O2 collected and the molar

mass of O2, respectively.
Rearranging the equation we obtain

Check The density of the oxygen gas is (0.164 g/0.128 L), or

1.28 g/L, which is a reasonable value for gases under
atmospheric conditions
 Chemistry in Action:
Scuba Diving and the Gas Laws
Depth (ft) Pressure
(atm)
0 1

33 2

66 3

P V

87
KINETIC MOLECULAR THEORY OF
GASES

88
 Postulates of the Kinetic-Molecular Theory
Postulate 1: Particle Volume
Because the volume of an individual gas particle is small compared to
the volume of its container, the gas particles are considered to have
mass, but no particle volume.

Postulate 2: Particle Motion

Gas particles are in constant, random, straight-line motion, colliding
frequently with each other or with the container walls, exerting pressure
to the container.
Postulate 3: Particle Collisions
Collisions are elastic, therefore, the total kinetic energy (Ek) of the
particles before collision is the same as that after collision. No attractive
or repulsive forces between the particles.
The average kinetic energy of the molecules is proportional to the
temperature of the gas in Kelvins. Any two gases at the same
temperature will have the same average kinetic energy
EK = ½ mu2 Where m: mass, u: speed
 Relationship of KMT to the gas laws
• Compressibility of Gases
Gas can be compressed as it does not have volume
(assumption 1)
• Boyle’s Law
P a collision rate with wall of gas container
Collision rate a number density
Number density a 1/V
P a 1/V
• Charles’s Law
P a collision rate with wall of gas container
Collision rate a average kinetic energy of gas molecules
Average kinetic energy a T
PaT 90
 Relationship of KMT to the gas laws
• Avogadro’s Law
P a collision rate with wall of gas container
Collision rate a number density
Number density a n
Pan

• Dalton’s Law of Partial Pressures

Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = SPi
91
 Molecular Speed vs. Molar Mass

• To have the same average kinetic energy, heavier

molecules must have a slower average speed
 Molecular Velocities
• All the gas molecules in a sample can travel at different
speeds.
• The distribution of speeds follows a statistical pattern, the
“average velocity” of the molecules.
• The method of average velocity is called the root-mean-
square method, where the rms average velocity, urms, is the
square root of the average of the sum of the squares of all the
molecule velocities.
• As the absolute temperature increases,
the average velocity increases
– the distribution function “spreads
out,” resulting in more molecules
with faster speeds
 Temperature and Molecular Velocities

• KEavg = ½NAmu2
– NA is Avogadro’s number
• KEavg = 1.5RT
– R is the gas constant in energy units, 8.314 J/mol∙K
• 1 J = 1 kg∙m2/s2
• Equating and solving we get
– NA∙mass = molar mass in kg/mol

• As temperature increases, the average velocity increases

MAXWELL SPEED DISTRIBUTION CURVES
urms = M 3RT

The distribution of speeds

of three different gases
at the same temperature
Lighter molecules are moving faster

The distribution of speeds

for nitrogen gas molecules
at three different temperatures
More molecules are moving faster at
higher temperature

95
Root-mean-square speeds

urms =  3RT
M

Where;
R = 8.314 J/K · mol
T = Temperature (K)
M = Molar mass (kg/mol)
Calculate the root-mean-square speeds of helium atoms and
nitrogen molecules in m/s at 25°C.
Strategy To calculate the root-mean-square speed we need
Equation
urms = M
3RT

What units should we use for R and so that urms will be

expressed in m/s?

Solution
To calculate urms, the units of R should be 8.314 J/K · mol and,
because 1 J = 1 kg m2/s2, the molar mass must be in kg/mol.

The molar mass of He is 4.003 g/mol, or 4.003 × 10−3 kg/mol.

Using the conversion factor 1 J = 1 kg m2/s2 we get
The procedure is the same for N2, the molar mass of which is
28.02 g/mol, or 2.802 × 10−2 kg/mol so that we write

Check
Because He is a lighter gas, we expect it to move faster, on
average, than N2. A quick way to check the answers is to note
that the ratio of the two urms values (1.36 × 103/515 ≈ 2.6)
should be equal to the square root of the ratios of the molar
masses of N2 to He, that is, .
GRAHAM’S LAW OF DIFFUSION &
EFFUSION

101
 Diffusion and Effusion
• The process of a collection of molecules spreading out from
high concentration to low concentration is called diffusion.
• The process by which a collection of molecules escapes
through a small hole into a vacuum is called effusion.
• The rates of diffusion and effusion of a gas are both related
to its rms average velocity.
• For gases at the same temperature, this means that the rate
of gas movement is inversely proportional to the square root
of its molar mass.
 Graham’s Law of Effusion
Thomas Graham (1805–1869)

• For two different gases at the same temperature,

the ratio of their rates of effusion is given by the
following equation:
Gas diffusion is the gradual mixing of molecules (molecules
spreading out) of one gas with molecules of another by virtue of
their kinetic properties.


r1 M2
=
r2 M1

molecular path
NH4Cl

NH3 is lighter,
diffuses faster.
Solid NH4Cl appears
at HCL bottle first.
NH3 HCl
17 g/mol 36 g/mol
104
Gas effusion is the process by which gas under pressure
escapes from one compartment of a container to another by
passing through a small opening.


r1 t2 M2
= =
r2 t1 M1

105
A flammable gas made up only of
carbon and hydrogen is found to
effuse through a porous barrier in
1.50 min.

Under the same conditions of

temperature and pressure, it
takes an equal volume of bromine
vapor 4.73 min to effuse through
the same barrier.
Gas effusion. Gas molecules
move from a high-pressure
Calculate the molar mass of the region (left) to a low-pressure
unknown gas, and suggest what one through a pinhole.
this gas might be.
Strategy The rate of diffusion is the number of molecules
passing through a porous barrier in a given time.

The longer the time it takes, the slower is the rate.

Therefore, the rate is inversely proportional to the time required

for diffusion.

Equation (5.17) can now be written as r1/r2 = t2/t1 = ,

where t1 and t2 are the times for effusion for gases 1 and 2,
respectively.
Solution From the molar mass of Br2, we write


r1 t2 M2
= =
r2 t1 M1
Where is the molar mass of the unknown gas. Solving for
we obtain

Because the molar mass of carbon is 12.01 g and that of

hydrogen is 1.008 g, the gas is methane (CH4).
Sample Problem 5.13 Applying Graham’s Law of Effusion

PROBLEM: A mixture of helium (He) and methane (CH4) is placed in an

effusion apparatus. Calculate the ratio of their effusion rates.

PLAN: The effusion rate is inversely proportional √M for each gas, so

we find the molar mass for each substance using its formula and
take the square root. The ratio of the effusion rates is the
inverse of the ratio of these square roots.

SOLUTION: M of CH4 = 16.04 g/mol M of He = 4.003 g/mol

rate

rate
He

CH4
= √ 4.003
16.04
= 2.002
REAL GASES; DEVIATIONS FROM
IDEAL BEHAVIOR

110
 Real Gases; Deviations from Ideal Behavior
• The kinetic-molecular model describes the behavior of ideal
gases. Ideal gas laws assume:
1. no attractions between gas molecules
2. gas molecules do not take up space
 based on the kinetic-molecular theory
• At low temperatures and high pressures these assumptions
are not valid.
• Real gases deviate from this behavior.
• Real gases have real volume.
– Gas particles are not points of mass, but have volumes determined by
the sizes of their atoms and the bonds between them.
• Real gases do experience attractive and repulsive forces
between their particles.
• Real gases deviate most from ideal behavior at low
temperature and high pressure.
 Real Gases; Deviations from Ideal Behavior

1 mole of ideal gas

Repulsive Forces
PV = nRT
PV = 1.0
n=
RT
Attractive Forces

112
The effect of interparticle attractions on
measured gas pressure.
The effect of particle volume on measured gas volume.
Van der Waals equation
Real gas
an 2
( P + V2 )(V – nb) = nRT
}

corrected }
corrected
pressure volume

Constant a relates to factors

that influence the attraction
between particles
(intermolecular forces).

Constant b relates to particle

volume.

115
Given that 3.50 moles of NH3 occupy 5.20 L at 47°C, calculate
the pressure of the gas (in atm) using

(a) the ideal gas equation and

(b) the van der Waals equation.

Strategy
To calculate the pressure of NH3 using the ideal gas equation,
we proceed as in Example 5.3.

What corrections are made to the pressure and volume terms in

the van der Waals equation?
Solution
(a) We have the following data:
V = 5.20 L
T = (47 + 273) K = 320 K
n = 3.50 mol
R = 0.0821 L · atm/K · mol
Substituting these values in the ideal gas equation, we write
(b) We need Equation (5.18). It is convenient to first calculate
the correction terms in Equation (5.18) separately. From
Table 5.4, we have

a = 4.17 atm · L2/mol2

b = 0.0371 L/mol

so that the correction terms for pressure and volume are

Finally, substituting these values in the van der Waals equation,
we have

Check Based on your understanding of nonideal gas behavior,

is it reasonable that the pressure calculated using the van der
Waals equation should be smaller than that using the ideal gas
equation? Why?
COLLIGATIVE PROPERTIES OF
PROPERTIES

121
• Colligative properties are properties that
depend only on the number of solute particles in
solution and not on the nature of the solute
particles.

• There are four colligative properties to

consider:
– Vapor pressure lowering (Raoult’s Law)
– Freezing point depression
– Boiling point elevation
– Osmotic pressure (not in syllabus)

122
 Vapor Pressure Lowering

• A solvent in a closed container reaches

a state of dynamic equilibrium.

• The pressure exerted by the vapor in

Initially, no molecules of the liquid
the headspace is referred to as the are in the gas phase. Zero vapor
vapor pressure of the solvent. pressure

• The addition of any nonvolatile solute

(one with no measurable vapor
pressure) to any solvent reduces the
vapor pressure of the solvent.
Vapor pressure that does not change as
long as the temperature remains constant.
At equilibrium,
Pgas = equilibrium at vapor pressure rate molecules leave the surface =
rate gas molecules return to liquid phase
 Vapor Pressure Lowering

• Raoult’s Law:
PA = XAPOA

where PA = partial pressure of the solvent vapor

above the solution (i.e with the solute)

XA = mole fraction of the solvent

PoA = vapor pressure of the pure

solvent
 Vapor Pressure Lowering

• Raoult’s Law breaks down when solvent-

solvent and solute-solute intermolecular
forces of attraction are much stronger or
weaker than solute-solvent intermolecular
forces.
Calculate the vapor pressure of a solution made by dissolving
218 g of glucose (molar mass = 180.2 g/mol) in 460 mL of water
at 30°C.

What is the vapor-pressure lowering?

The vapor pressure of pure water at 30°C is given in Table 5.3

(p. 199). Assume the density of the solvent is 1.00 g/mL.
Strategy We need Raoult’s law [Equation (12.4)] to determine
the vapor pressure of a solution. Note that glucose is a
nonvolatile solute.

Solution The vapor pressure of a solution (P1) is

First we calculate the number of moles of glucose and water in

the solution:
The mole fraction of water, X1, is given by

From Table 5.3, we find the vapor pressure of water at 30°C to

be 31.82 mmHg. Therefore, the vapor pressure of the glucose
solution is
P1 = 0.955  31.82 mmHg
= 30.4 mmHg

Finally, the vapor-pressure lowering (DP) is

(31.82 − 30.4) mmHg, or 1.4 mmHg.
Exercise
The vapor pressure of water at 20oC is 17.5 torr.
Calculate the vapor pressure of an aqueous solution
prepared by adding 36.0 g of glucose (C6H12O6) to 14.4
g of water.

Answer: 14.0 torr

129
Exercise
The vapor pressure of pure water at 110oC is 1070 torr.
A solution of ethylene glycol and water has a vapor
pressure of 1.10 atm at the same temperature. What is
the mole fraction of ethylene glycol in the solution?

Answer: XEG = 0.219

130
 Vapor Pressure Lowering

• The vapor pressure of a solvent in a solution is

always lower than the vapor pressure of the pure
solvent
• The vapor pressure of the solution is directly
proportional to the amount of the solvent in the
solution
• The difference between the vapor pressure of the
pure solvent and the vapor pressure of the solvent
in solution is called the vapor pressure lowering
DP = Pºsolvent − Psolution = csolute  Pºsolvent
 Vapor Pressure Lowering

• Ideal solutions are those that obey Raoult’s

Law.

• Real solutions show approximately ideal

behavior when:
– The solution concentration is low
– The solute and solvent have similarly sized
molecules
– The solute and solvent have similar types
of intermolecular forces.
 Raoult’s Law for Volatile Solute

• When both the solvent and the solute can evaporate, both
molecules will be found in the vapor phase
• The total vapor pressure above the solution will be the sum
of the vapor pressures of the solute and solvent
– for an ideal solution
Ptotal = Psolute + Psolvent
• The solvent decreases the solute vapor pressure in the
same way the solute decreased the solvent’s
Psolute = csoluteP°solute and Psolvent = csolventP°solvent
Ideal Solution PA = XA P A0
PB = XB P B0
PT = PA + PB
PT = XA P A0 + XB P 0B

134
 Vapor Pressure Lowering

• Nonvolatile solutes reduce the ability of the

surface solvent molecules to escape the
liquid.
– Vapor pressure is lowered.

• The extent of vapor pressure lowering

depends on the amount of solute.
– Raoult’s Law quantifies the amount of
vapor pressure lowering observed.
 Boiling Point Elevation
• The addition of a nonvolatile solute causes
solutions to have higher boiling points than the
pure solvent.
– Boiling point define as a temperature at which
the vapor pressure of the liquid equals the pressure
surrounding the liquid and the liquid changes into a
vapor.

– Vapor pressure decreases with addition of non-volatile

solute.

– Higher temperature is needed in order for vapor

pressure to equal 1 atm.
 BP Elevation
• The boiling point of a solution is higher than the
boiling point of the pure solvent
– for a nonvolatile solute
• The difference between the boiling point of the
solution and boiling point of the pure solvent is
directly proportional to the molal concentration of
solute particles
(BPsolution – BPsolvent) = DTb = Kbm
• The proportionality constant is called the Boiling
Point Elevation Constant, Kb
– the value of Kb depends on the solvent
– the units of Kb are °C/m
Boiling-Point Elevation
DTb = Tb – T b0
0
T b is the boiling point of
the pure solvent

T b is the boiling point of

the solution

Tb > T b0 DTb > 0

DTb = Kb m
m is the molality of the solution

Kb is the molal boiling-point

elevation constant (0C/m)
for a given solvent
138
 Freezing Solution

A good example of a “frozen

solution” is ice popsicle.

What happens to an ice popsicle

if you suck on it ?

Right !. A very sweet liquid come

out, and all you have left is a
tasteless stick of water ice.
 Freezing Salt Water
• Pure water freezes at 0 ºC.
• At this temperature, ice and liquid water are in dynamic
equilibrium.
• Adding salt disrupts the equilibrium. The salt particles
dissolve in the water, but do not attach easily to the solid
ice.
• When an aqueous solution containing a dissolved solid
solute freezes slowly, the ice that forms does not normally
contain much of the solute.
• To return the system to equilibrium, the temperature must
be lowered sufficiently to make the water molecules slow
down enough so that more can attach themselves to the
ice.
 Freezing Point Depression

• The freezing point of a solution is lower than the

freezing point of the pure solvent
– therefore the melting point of the solid solution is lower
• The difference between the freezing point of the
solution and freezing point of the pure solvent is
directly proportional to the molal concentration of
solute particles
(FPsolvent – FPsolution) = ∆Tf = Kfm
• The proportionality constant is called the Freezing
Point Depression Constant, Kf
– the value of Kf depends on the solvent
– the units of Kf are °C/m
 Freezing Point Depression
• The addition of a nonvolatile solute causes
solutions to have lower freezing points than the
pure solvent.
– Freezing point define as a temperature at which a
liquid of specified composition solidifies under a
specified pressure

– Solid-liquid equilibrium line rises ~ vertically from the

triple point, which is lower than that of pure solvent.

– Freezing point of the solution is lower than that of the

pure solvent
Freezing-Point Depression
DTf = T 0f – Tf
T f0 is the freezing point of
the pure solvent

T f is the freezing point of

the solution

T 0f > Tf DTf > 0

DTf = Kf m
m is the molality of the solution

Kf is the molal freezing-point

depression constant (0C/m)
for a given solvent
143
Difference of Kf and Kb
Ethylene glycol (EG), CH2(OH)CH2(OH), is a common
automobile antifreeze. It is water soluble and fairly nonvolatile
(b.p. 197°C).

Calculate the freezing point of a solution containing 651 g of

this substance in 2505 g of water.

Would you keep this substance in your car radiator during the
summer?

The molar mass of ethylene glycol is 62.01 g.

Strategy This question asks for the depression in freezing
point of the solution.

The information given enables us to calculate the molality of the

solution and we refer to Table 12.2 for the Kf of water.

Solution To solve for the molality of the solution, we need to

know the number of moles of EG and the mass of the solvent in
kilograms.
We fi nd the molar mass of EG, and convert the mass of the
solvent to 2.505 kg, and calculate the molality as follows:

From Equation (12.7) and Table 12.2 we write

Because pure water freezes at 0°C, the solution will freeze at
(0 − 7.79)°C or 27.79°C.

We can calculate boiling-point elevation in the same way as

follows:

Because the solution will boil at (100 + 2.2)°C, or 102.2°C, it

would be preferable to leave the antifreeze in your car radiator
in summer to prevent the solution from boiling.
Exercise
Calculate the boiling point of an aqueous solution that
contains 20.0 mass % ethylene glycol (C2H6O2, a
nonvolatile liquid).

BP = 102.1oC
149
Exercise
Calculate the freezing point depression of a solution that
contains 5.15 g of benzene (C6H6) dissolved in 50.0 g of
CCl4.

150
PHASE DIAGRAM
The Structure and Properties of Water
The unique macroscopic behavior of water that emerges from its
atomic and molecular properties
 The Unique Nature of Water
• great solvent properties due to polarity and
hydrogen bonding ability

• exceptional high specific heat capacity

• high surface tension and capillarity

• density differences of liquid and solid states

 H-bonding ability of water
hydrogen bond donor

hydrogen bond acceptor

Each H2O molecule can form four H bonds to other molecules,

resulting in a tetrahedral arrangement.
The hexagonal structure of ice

• Ice has an open structure due to H bonding.

Ice is therefore less dense than liquid water.
3-D Structure of Water
Water is a Unique Substance

Maximum Density
40C
Density of Water

Ice is less dense than water

156
 Phase Changes
• When a substance changes from solid to
liquid to gas, the molecules remain intact.
• The changes in state are due to changes
in the forces among molecules rather than
in those within the molecules.
 Phase Changes
sublimation

vaporizing exothermic
melting

solid liquid gas

endothermic
freezing condensing

deposition
 Heating Curve of Water
Temperature

4
100oC

0oC
2
-25oC 1

159
SEGMENT 1- Ice warming
 Solid ice is warmed from -250C to 00C
No phase transition occurs here
SEGMENT 2- Ice melting to liquid water
1st transition: solid - liquid
Temperature does not change during melting
Liquid and solid coexist at 00C
SEGMENT 3- Liquid water warming
Liquid water is warmed from 00C to 1000C
SEGMENT 4- Liquid water vaporizing into steam
2nd transition: liquid – gas
Temperature does not change during boiling
Liquid and gas coexist at 1000C
SEGMENT 5- Steam warming
Solid ice is warmed from 1000C to 1250C
No phase transition occurs here
 Phase Diagram
• A phase diagram summarizes the conditions at
which a substance exists as a solid, liquid, or
gas.
• A convenient way of representing the phases of
a substance as a function of temperature and
pressure:
 Triple point
 Critical point
 Phase equilibrium lines
01Phase_Diagram.mov
Triple point
• The point on a phase diagram representing the
temperature and pressure at which three phases
of a substance coexist in equilibrium.

Critical point-
• The point where system is at its critical pressure
and temp
Critical pressure (Pc)
• the minimum pressure that must be applied to bring
about liquefaction at the critical temperature
• vapor pressure at critical temp.
Critical temperature (Tc)
• the temperature above which the gas cannot be made
to liquefy, no matter how great the applied pressure
• Temp. where substance must always be gas, no matter
what pressure.
Phase Diagram of Water
A NEGATIVE SLOPE of
solid-liquid boundary
line:
The molar volume of ice
is greater than that of
liquid water hence water
is denser than ice.
An increase in pressure
favors the liquid phase.

Triple point of water:

At T :0.01°C
P :0.006 atm

165
Effect of Increase in Pressure on the Melting Point of
Ice and the Boiling Point of Water

166
Phase Diagram of Carbon
Dioxide
A POSITIVE SLOPE of
solid-liquid boundary line:
Almost all other substances
have the positive slope of
solid-liquid boundary line.

Liquid phase of CO2

well above atmosphere
pressure which above
5.2 atm

Triple point of CO2:

At T : - 57 °C
P : 5.2 atm

167
 The Dry Ice (CO2 (s) )
• It is very useful as a
refrigerant
• It looks like ice and
does not melt
• Sublimation process
occur when solid
CO2 is heated to -78
°C at 1 atm. At 1 atm
CO2 (s) CO2 (g)
 Concept check
What phase exists at the point labeled a,b and
c?
P (atm)

a
1 b

10 20 30 40 50 60 70 80 90
T (°C)
 Concept check
Shown below is a phase diagram for
compound Y. At 25°C and 1 atm Y will exist
as a ________:
P (atm)

1 a b c

10 20 30 40 50 60 70 80 90
T (°C)
Based on the phase diagram shown below, which of the following statements are
correct?
I. Sublimation occurs at a point in the transformation that occurs along a straight line
from point A to point F.
II. C and E represent points where the gas and liquid phases are in equilibrium.
III. Hvap can be measured at point B.
IV. Molecules at point D have a greater average kinetic energy than those at point F.
V. The temperature at point E is called the critical temperature of the compound.

a) II, V
b) I, III, IV
c) I, II, III
d) II, IV, V
e) I, II, IV