Syllabus

Chemistry 102 Spring 2011

Sec. 501, 503 (MWF 8-8:50,
12:40-1:30)
RM 100 HELD
Professor: Dr. Earle G. Stone
Office: Room 123E Heldenfels (HELD)
Telephone: 845-3010 (no voice mail) or leave
message at 845-2356
email: stone@mail.chem.tamu.edu
(put CHEM 101-Sec. # + subject in subject line of
your email)

All

College
BIMS
Science
GEST and other
Agriculture other
Engineering
Ag BICH, NUSC,
GENE
Education
Liberal Arts
Geosciences
Architecture
Business and other

459
133
114
56
25
50

100%
29%
25%
12%
5%
11%

27
15
17
15
0
5

6%
3%
4%
3%
0%
1%

501

College
Science
GEST and other
BIMS
Engineering
Agriculture other
Ag BICH, NUSC,
GENE
Liberal Arts
Education

2014
2013
2012
2011
2010
graduate

240
165
32
18
2
2
459

86% pre-something
14% widely diverging
academic foci
503

199
50
24
56
24
9

100%
25%
12%
28%
12%
5%

College
BIMS
Science
GEST and other
Agriculture other
Education

260
77
64
34
16
9

100%
30%
25%
13%
6%
3%

13
7

7%
4%

26
10

10%
4%

3%

Engineering
Liberal Arts
Ag BICH, NUSC,
GENE
Business and

14

5%

Kotz and Treichel 7th ed.

TEXTBOOKS

Averill and

Hardbound
~$200
Solution Manual
~$40
Online Tutor
~$45
Total
~$285
Ebook $45 per
semester
Yvette Freeman
Publisher's Representative
Includes
Pearson Education
Text
Yvette.Freeman@Pearson.com
Helpful
Solution
Online Dictionary of Chemistry
manual
Useful
Online
As A Second Language
General Chemistry I and
tutorial
Organic Chemistry I
(There are O-chem II and Physics

books in this series if you find

these
classes.
Changs Essentials

useful and will have to take those

http://slc.tamu.edu/
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Courses
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How grades are determin

A+
+
A+
A
B
C
D
F
F-

1)
2)
3)
4)

The way the real world

works
Individual Mastery
compared
to a large population
What you are used to and
Normal Exam 1 Exam 2 Exam 3 Exam 4 Final
I will
>3 0.1%
0.0%
0.0%
0.0%
0.0% 0.0%
report

>2
>1
>0
<0
<-1
<-2
<-3

2.1%
13.6%
34.1%
34.1%
13.6%
2.1%
0.1%

1.4%
18.5%
32.7%
31.3%
14.7%
1.4%
0.0%

0.4%
19.9%
33.7%
28.7%
14.9%
1.0%
0.0%

0.6%
13.5%
25.7%
34.1%
20.9%
1.8%
0.0%

0.0%
0.0%
0.0%
0.0%
0.0%
0.0%
0.0%

0.0%
0.0%
0.0%
0.0%
0.0%
0.0%
0.0%

Raw scores are determined.

Sum of points assigned
Individual scores are normalized.
A context-free evaluatio
Normalized scores are transformed.
An absolute score is assigned
Letter grades are assigned
>89.501 A
>79.501 B
>69.501 C
>59.501 D
<59.501 F

Grading:
Your grade will be based on
Four one-hour examinations (200 raw points
T score 100+)
A final examination (400 raw points 2 x T
score
100+) Examination Schedule
Major

Spring 2011:
Major Exam No.1

Mon. Feb. 7

Major Exam No.2

Wed. Mar. 2

Major Exam No.3

Wed. Apr. 13

Major Exam No.4

Fri. Apr. 29

Final Exams
Section 501
Fri. May 6, 10:00 to

Section 503
Mon. May 9, 10:30

The mere formulation of a problem is

far more often essential than its
solution, which may be merely a
matter
of
mathematical
or
experimental skill. To raise new
questions, new possibilities, to regard
old problems from a new angle
requires creative imagination and
marks real advances in science.
~Albert Einstein
Problem - A situation that presents difficulty,
uncertainty, or perplexity:
Question - A request for data: inquiry, interrogation,
query.
Answer - A spoken or written reply, as to a question.
Solution - Something worked out to explain, resolve, or

1. Numbers Significant Figures, Rounding Rules, Accuracy,

Precision, Statistical Treatment of the Data
2. Units 5 of the 7
1. Time seconds
2. Length Meters
Density?
3. Mass grams
Molecular Weight (Mass)
4. Amount Moles
Mole Ratio,
Molarity, molality
5. Temperature Kelvins
3. Vocabulary Approximately 100 new terms or words and
applying new or more rigid definitions to words you may
already own.
4. Principles (Theories and Laws) Stoichiometry, Quantum
Theory, Bonding, Chemical Periodicity, Solutions,
Thermodynamics, Intermolecular Forces, Gas Laws,
Collogative Properties, Kinetics, Equilibrium,
[C]c[D]d
Electrochemistry
a
b
[A]
[D]
-1
c (ms )
E =
(m)
cp = q/mT
rate
= k[A]m[B]n

Last Semester you studied

Interforces holding atoms together

molecula
to form molecules.
Now turn to forces between
r Forces
INTRAmolecular forcesthe

molecules

INTERmolecular forces.
Forces between molecules,
between ions, or between
molecules and ions.

Ion-Ion Forces
for comparison of
magnitude
Na+Cl- in salt
These are the
strongest forces.
Lead to solids with
high melting
temperatures.
NaCl, mp = 800 oC
MgO, mp = 2800 oC

Ion Permanent
Dipole
Attractions

water
dipole

O
H
H +

Water is highly polar and

can interact with positive
ions to give
in water.

hydrated ions

Attraction
Between Ions and
Permanent
Dipoles
Many metal
ions are hydrated.
This is the reason metal
salts dissolve in water.

Attraction
Between Ions and
Permanent
Dipoles
Attraction between ions and dipole depends on
ion charge and ion-dipole distance.
Measured by H for Mn+ + H2O --> [M(H2O)x]n+

H
O
H
+

Mg2+

H
O
H
+

H
O
H
+

Na +

-1922 kJ/mol -405 kJ/mol

Cs+

-263 kJ/mol

Dipole-Dipole
Forces
Such forces bind molecules having
permanent dipoles to one another.
Influence of dipole-dipole
forces is seen in the boiling
points of simple molecules.
Compd
Mol. Wt. Boil Point
N2
28
-196 oC
CO
Br2

28
160

-192 oC
59 oC

ICl

162

97 oC

Interactions in Liquid
Hydrophilic and hydrophobic
solutes
Solutions

A solute can be classified as hydrophilic, meaning that there is an electrostatic

attraction to water, or hydrophobic, meaning that it repels water.

1. Hydrophilic substance is polar and contains OH or NH groups that can form hydrogen bonds to water;
tend to be very soluble in water and other strongly polar solvents
2. Hydrophobic substance may be polar but usually contains CH bonds that do not interact favorably with
water; essentially insoluble in water and soluble in nonpolar solvents

The difference between hydrophilic and hydrophobic substances has substantial

consequences in biological systems.
Vitamins can be classified as either fat soluble or water soluble.
1. Fat-soluble vitamins (Vitamin A) are nonpolar, hydrophobic molecules and tend to be absorbed into fatty
tissues and stored there.
2. Water-soluble vitamins (Vitamin C) are polar, hydrophilic molecules that circulate in the blood and
intracellular fluids and are excreted from the body and must be replenished in the daily diet.

Ionic substances are most stable in polar solvents.

Water is the most common solvent for ionic compounds because of its high polarity.
A more useful measure of the ability of a solvent to dissolve ionic compounds is its dielectric
constant (), which is the ability of a bulk substance to decrease the electrostatic forces between
two charged particles.

Hydrogen Bonding
A special form of dipole-dipole attraction,
which enhances dipole-dipole attractions.

H-bonding is
especially strong
in water because
the OH bond is
very polar
there are 2 lone
pairs on the O
atom
Accounts for many
of waters unique
properties.

H-bonding is strongest when X and Y are

N, O, or F

Hydrogen Bonding in
H2O

Ice has open lattice-like structure.

Ice density is < liquid and so solid floats on water.

One of the VERY

few substances
where solid is
LESS DENSE than
the liquid.

H bonds abnormally high specific heat capacity of

water (4.184 J/gK)
This is the reason water is used to put out fires, it is the
reason lakes/oceans control climate, and is the reason

Boiling Points of
Simple HydrogenContaining
Compounds

Active Figure 13.8

Double helix
of DNA

Portion of a
DNA chain
H-bonding is especially strong in biological systems such as
DNA.
DNA helical chains of phosphate groups and sugar molecules.
Chains are helical because of tetrahedral geometry of P, C, and O.
Chains bind to one another by specific hydrogen bonding between
pairs of Lewis bases.

Base-Pairing through HBonds

Base-Pairing through HBonds

FORCES INVOLVING
INDUCED DIPOLES

How can non-polar molecules such as O 2 and I2 dissolve in water?

The water dipole INDUCES a

dipole in the O2 electric cloud.

Dipole-induced
Dipole-induced
dipole
dipole

FORCES INVOLVING INDUCED

DIPOLES
Consider I
2

dissolving
in ethanol,
I-I CH3CH2OH.

R
Solubility increases with mass the gas

O
H

The alcohol
temporarily
creates or
INDUCES a
dipole in I2.

I-I
+

O
H
+

Process of inducing a dipole is polarization

Degree to which electron cloud of an atom or molecule can be distorted in
its polarizability.
Non-polar gases are most soluble in non-polar solvents.

FORCES INVOLVING
INDUCED DIPOLES
Formation of a dipole in two nonpolar I2
molecules.
Induced dipole-induced dipole

The induced forces between I2 molecules are very weak, so

solid I2 sublimes (goes from a solid to gaseous molecules).

FORCES INVOLVING
INDUCED DIPOLES
The magnitude of the induced dipole
depends on the tendency to be distorted.
Higher molec. weight larger induced
dipoles.
Molecule
Boiling Point (oC)
CH4 (methane)
- 161.5
C2H6 (ethane) - 88.6
C3H8 (propane)

- 42.1

C4H10 (butane)

- 0.5

Intermolecular Forces
Summary

London dispersion forces, dipole-dipole interactions, and hydrogen

bonds that hold molecules to other molecules are weak.
Energy is required to disrupt these interactions, and unless some
of that energy is recovered in the formation of new, favorable
solute-solvent interactions, the increase in entropy on solution

Vapor Pressure
When the liquid is heated, its molecules obtain sufficient kinetic energy to
overcome the forces holding them in the liquid and they escape into the
gaseous phase.
The result of this phenomenon is that the molecules from the liquid phase
generate a population of molecules in the vapor phase above the liquid that
produces a pressure called the vapor pressure of the liquid.
Plotting the fraction of molecules with a given KE against their KE gives
the KE distribution of the molecules in the liquid.
Increasing the temperature increases both
the average KE of the particles in a liquid
and the range of KE for the molecules.
Molecules with KE greater than Eo
can escape from the liquid to enter
the vapor phase
Molecules must also be at the surface
where it is physically possible for the
molecule to leave the liquid surface.

Equilibrium Vapor Phase

Volatile liquids have high vapor pressures and tend to
evaporate readily; nonvolatile liquids have low vapor
pressures and evaporate more slowly.
Substances with vapor pressures higher than that of water
are volatile, whereas those with vapor pressures lower
than water are nonvolatile.
Equilibrium vapor pressure of a substance at a particular
temperature is a characteristic of the material.
Does not depend on the amount of liquid
Depends strongly on the temperature and intermolecular
forces

Liquids Equilibrium Vapor

Pressure
VP as a function of T.
1. The curves show all conditions of P and T where LIQ
and VAP are in EQUILIBRIUM
2. The VP rises with T.
3. When VP = external P, the liquid boils.
This means that BPs of liquids change with altitude.
4. If external P = 760 mm Hg, T of boiling is the NORMAL
BOILING POINT
5. VP of a given molecule at a given T depends on IM forces.
Here the VPs are in the order
ether
O
H5C2

alcohol
O
C2H5

dipole dipole

H5C2
Hbonds

water
O
H

extensive Hbonds

increasingstrengthofIMinteractions

Liquids
HEAT OF VAPORIZATION is the heat reqd
(at constant P) to vaporize the liquid.
LIQ + heat VAP
Compd.
Hvap (kJ/mol) IM Force
H 2O
bonds
SO2

40.7 (100 oC)

Xe
dipole

12.6 (-107 oC)

26.8 (-47 oC)

Hdipole
induced

Phase Diagrams

Lines connect all conditions of T and P where EQUILIBRIUM exists

between the phases on either side of the line. (At equilibrium
particles move from liquid to gas as fast as they move from gas to
liquid, for example.)

Phase Equilibria
Water

Solid-liquid

Gas-Liquid

Gas-Solid

Triple
Point
Water

At the TRIPLE POINT all

three phases are in
equilibrium.

Phases Diagrams
Important Points
for Water

T(C)
P(mmHg)
Normal boil point
100
Normal freeze point 0
Triple point
0.0098

760
760
4.58

Critical T and P
As P and T increase, you finally reach the CRITICAL T and P

Pcritical

Notethatline
goesstraightup

HighPressure

LIQUID

GAS
HighTemperature

Above critical T no
liquid exists no
matter how high the
pressure. The gas
Tcritical
and liquid phases are
intermixed and
indistinguishable.

At P < 4.58 mmHg and T < 0.0098 C solid H2O

can go directly to vapor. This process is called
SUBLIMATION
This is how a frost-free refrigerator works.

Terminology and
Supercritical Fluids
Critical temperature (Tc)

Temperature above which the gas can no longer be liquefied,

regardless of pressure
The highest temperature at which a substance can exist as a liquid
Above the critical temperature, the molecules have too much kinetic
energy for the intermolecular attractive forces to hold them together in a
separate liquid phase
Critical pressure (Pc)

Minimum pressure needed to liquefy a substance at the critical

temperature
Critical point combination of critical temperature and critical pressure
As the temperature of a liquid increases, its density decreases.
As the pressure of a gas increases, its density increases.
At the critical point, the liquid and gas phases have exactly the same
density, and only a single phase exists, called a supercritical fluid, which
exhibits many of the properties of a gas but has a density typical of a liquid.

Solid-Liquid Equilibria
ICE
P
Solid
H 2O

Liquid
H 2O

favoredat
lowP
Normal
freezing
point

760
mmHg
0C

LIQUIDH 2O
favoredat
highP

Raising the pressure at constant

T causes water to melt.
The NEGATIVE SLOPE of the S/L
line is unique to H2O. Almost
everything else has positive
slope.

T
The behavior of water under pressure is an example of LE
CHATELIERS PRINCIPLE At Solid/Liquid equilibrium,
raising P squeezes the solid.
It In
responds
by going to phase with greater density, i.e., the
any system, if you increase P the DENSITY will go up.
liquid
phase.
Therefore
as P goes up, equilibrium favors phase with
the larger density (or SMALLER volume/gram).

Changes of State
Changes of state are examples of phase changes,
or phase transitions
Any of the three forms of matter (gas, liquid,
solid) is converted to either of the other two
Six most common phase changes:
1. melting
solid liquid
2. freezing
liquid solid
3. vaporization
liquid gas
4. condensation
gas
liquid
5. sublimation
solid gas
6. deposition
gas
solid

Temperatu
re Curves
Heating Curve A plot of temperature
versus time where heat is added

1. Sample is ice at -23C

2. As heat is added, the temperature of the ice increases linearly with time
3. Slope of the line depends on both the mass of the ice and the specific heat of ice, the number of
joules required to raise the temperature of 1 g of ice by 1C
4. As the temperature of the ice increases, the water molecules in the ice crystal absorb more and more
energy and at the melting point, they have enough kinetic energy to overcome attractive forces and
to move
5. As more heat is added, the temperature of the system does not increase further, but remains
constant at 0C until all the ice has melted
6. Once all the ice has been converted to liquid water, the temperature of the water begins to increase
temperature increases more slowly than before because the heat capacity of water is greater than
that of ice
7. At 100C, water begins to boil; temperature remains constant until all the water has been converted
to steam
8. Temperature again begins to rise, but at a faster rate because the heat capacity of steam is less than
that of ice or water

Temperature Curves

Cooling curves A plot of temperature vs. time when heat is

removed

1. As heat is removed from steam at 200C, the temperature falls until it

reaches 100C, where the steam begins to condense to liquid water
2. No further temperature change occurs until all the steam is converted to
the liquid; then the temperature again decreases as the water is cooled
3. Temperature drops below the freezing point for some time region
corresponds to an unstable form of the liquid, a supercooled liquid that
will convert to a solid
4. As water freezes, temperature increases due to heat evolved and then
holds constant at the melting point

Units of Concentration

There are several different ways to quantitatively describe the concentration of a

solution, which is the amount of solute in a given quantity of solution.

1. Molarity Useful way to describe solution concentrations for reactions that are carried out in solution or for
titrations. Volume of a solution depends on its density, which is a function of temperature
Molarity = moles of solute = mol/L = mmol/mL
liter of solution
2. Molality Concentration of a solution can also be described by its molality (m), the number of moles of solute
per kilogram of solvent. Depends on the masses of the solute and solvent, which are independent of temperature.
Molality = moles of solute
kilogram solvent
Mole fraction Used to describe gas concentrations and determine the vapor pressures of mixtures of similar
liquids. Depends on only the masses of the solute and solvent and is temperature independent. Mole fractions sum
to one for a given mixture.
Mole fraction ( ) =
moles of component
.
total moles in the solution
4. Mass percentage (%) The ratio of the mass of the solute to the total mass of the solution. Result can be
expressed as mass percentage, parts per million (ppm), or parts per billion (ppb). ppm and ppb are used for highly
dilute solutions, and correspond to milligrams (10-3) and micrograms (10-6) of solute per kilogram of solution,
respectively
mass percentage = mass of solute 100%
mass of solution
parts per million (ppm)= mass of solute 106
mass of solution
parts per billion (ppb)= mass of solute 109
mass of solution

Units of Concentration
Mass percentage and parts per million or
billion can express the concentrations of
substances even if their molecular mass is
unknown because these are simply different
ways of expressing the ratios of the mass of a
solute to the mass of the solution

Molality and Mole Fraction

Calculate the molarity and the molality of an aqueous solution
that is 10.0% glucose, C6H12O6. The density of the solution is
1.04 g/mL. 10.0% glucose solution has several medical uses. 1
mol C6H12O6 = 180 g

Molality and Mole

Calculate the molality of aFraction
solution that contains 7.25 g of benzoic acid
C6H5COOH, in 2.00 x 102 mL of benzene, C6H6. The density of benzene is
0.879 g/mL. 1 mol C6H5COOH = 122 g

Molality and Mole Fraction

What are the mole fractions of glucose and water in a 10.0%
glucose solution?

Vapor Pressure of Solutions

and
Raoults Law
The addition of a nonvolatile solute, one whose
vapor pressure is too low to measure readily, to a
volatile solvent decreases the vapor pressure of the
solvent.

The relationship between solution composition and

vapor is known as Raoults law,
PA = AP0 A,
where PA is the vapor pressure of component A of the
solution (the solvent), A is the mole fraction of A in
solution, and P0A is the vapor pressure of pure A.

This equation is used to calculate the actual vapor

pressure above a solution of a nonvolatile solute.

Vapor Pressure of Solutions

and
Raoults Law

Plots of the vapor pressures of both components versus the mole fractions are straight lines
that pass through the origin.
A plot of the total vapor pressure of the solution versus the mole fraction is a straight line that
represents the sum of the vapor pressures of the pure components.
The vapor pressure of the solution is always greater than the vapor pressure of either
component.
Solutions that obey Raoults law are called ideal solutions, in which the intermolecular
forces in the two pure liquids are almost identical in both kind and magnitude and the change
in enthalpy on solution formation is essentially zero (Hsoln 0).
Real solutions exhibit positive or negative deviations from Raoults law because the
intermolecular interactions between the two components A and B differ.

Negative deviation
If the AB interactions are stronger than the AA and BB interactions, each component of the solution
exhibits a lower vapor pressure than expected for an ideal solution, as does the solution as a whole.
The favorable AB interactions stabilize the solution compared with the vapor.
Positive deviation
If the AB interactions are weaker than the AA and BB interactions yet the entropy increase is enough
to allow the solution to form, both A and B have an increased tendency to escape from the solution into
the vapor phase.
The result is a higher vapor pressure than expected for an ideal solution.

Lowering of Vapor Pressure

and Raoults Law
Addition of a nonvolatile solute to a solution lowers the vapor
pressure of the solution.
The effect is simply due to fewer solvent molecules at the
solutions surface.
The solute molecules occupy some of the spaces that would
normally be occupied by solvent.
Raoults Law models this effect in ideal solutions.

This graph shows how the

solutions vapor pressure is
changed by the mole fraction
of the solute, which is
Raoults law.

Effect of Temperature on
the Solubility

Solubility of a substance generally increases with increasing temperature.

No relationship between the structure of a substance and temperature
dependence.
Solubility may increase or decrease with temperature; the magnitude varies
widely among compounds.
The variation of solubility with temperature is used to separate the components of
a mixture by fractional crystallization, a technique for purifying compounds.
For fractional crystallization to be effective the compound must be more soluble
at high T than at low T: lowering the temperature causes it to crystallize out of
solution.
Solubility of gases in liquids decreases with increasing temperature
Attractive intermolecular interactions in the gas phase are essentially zero for
most substances.
When a gas dissolves, its molecules interact with solvent molecules and heat is
released when these new attractive interactions form, therefore, dissolving most
gases in liquids is an exothermic process (Hsoln < 0)
Adding heat to the solution provides thermal energy that overcomes the attractive
forces between the gas and the solvent molecules, thereby decreasing the
solubility of the gas

Fractional Distillation
Distillation is a technique used
to separate solutions that have
two or more volatile components
with differing boiling points.
A simple distillation has a
single distilling column.
Simple distillations give reasonable
separations.

A fractional distillation gives

increased separations because
of the increased surface area.

Commonly, glass beads or steel wool

are inserted into the distilling
column.

Pressure and Solubility of

Gases: Henrys Law

External pressure has little effect on the solubility of liquids and solids. The
solubility of gases increases as the partial pressure of the gas above a solution
increases.

The concentration of molecules in the gas phase increases with increasing pressure, as
does the concentration of dissolved gas molecules in the solution at equilibrium at
higher pressures.
Henrys Law: C = kP, where C is the concentration of dissolved gas at equilibrium; P
is the partial pressure; and k is the Henrys law constant, which is determined
experimentally for each combination of gas, solvent, and temperature: units are M/atm.
Concentration of a gas in water at a given pressure depends strongly on its physical
properties.
Gases that react chemically with water do not obey Henrys law; all of these gases are
much more soluble than predicted by Henrys law

Colligative Properties of
Solutions

The colligative properties of a solution depend primarily on the number

of solute particles present rather than the kind of particles.
Not all solutions with the same molarity contain the same concentration
of solute particles.
The sum of the concentrations of the various dissolved solute particles
dictates the physical properties of a solution.
Colligative properties do not depend on the kinds of particles dissolved.
Colligative properties are a physical property of solutions.
There are four colligative properties:
1. Boiling-point elevation
2. Freezing-Point depression
3. Vapor pressure
4. Osmotic pressure
Vapor pressure lowering is the key to all four of the colligative properties.

Boiling-Point Elevation
The normal boiling point of a substance is the temperature at
which the vapor pressure equals 1 atm.
Because the vapor pressure of the solution at a given
temperature is lower than the vapor pressure of the pure solvent,
achieving a vapor pressure of 1 atm for the solution requires a
higher temperature than the normal boiling point of the solvent.
The boiling point of a solution is always higher than that of the
pure solvent.
The magnitude of the increase in the boiling point is related to
the magnitude of the decrease in the vapor pressure; the
decrease in the vapor pressure is proportional to the
concentration of the solute in solution.

Boiling Point Elevation

Addition of a nonvolatile solute to a solution raises the boiling

point of the solution above that of the pure solvent.
This effect is because the solutions vapor pressure is
lowered as described by Raoults law.
The solutions temperature must be raised to make the
solutions vapor pressure equal to the atmospheric
pressure.
The amount that the temperature is elevated is determined by
the number of moles of solute dissolved in the solution.

Boiling point elevation relationship

is:

Freezing Point
Depression
Dissolving a nonvolatile solute in water not only raises the
boiling point of the water but also lowers its freezing point.
Freezing-point depression depends on the total number of
dissolved nonvolatile solute particles.
The molar mass of an unknown compound can be determined by
measuring the freezing point of a solution that contains a known
mass of solute, which is accurate for dilute solutions.
Changes in the boiling point are smaller than changes in the
freezing point for a given solvent, so boiling point elevations are
difficult to measure and are not used to determine molar mass.
The freezing-point depression (Tf) is defined as the difference
between the freezing point of the pure solvent and the freezing
point of the solution:
Relationship for freezing point depression is:

Freezing Point
Depression

Colligative Properties of
Electrolyte Solutions

The relationship between the actual number of moles of solute added to

form a solution and the apparent number as determined by colligative
properties is called the vant Hoff factor (i) and is defined as
i = apparent number of particles in solution
number of moles of solute dissolved

The vant Hoff factors for ionic

compounds are lower than expected,
their solutions apparently contain
fewer particles than predicted by the
number of ions per formula unit.
Deviation from the expected value
increases as the concentration of the
solute increases because ionic
compounds do not totally dissociate in
aqueous solution.
Some of the ions exist as ion pairs, for
a brief time are associated with each.
The actual number of solvated ions
present in a solution can be

Freezing Point
Depression
Notice the similarity of the two relationships for freezing
point depression and boiling point elevation.

Fundamentally, freezing point depression and boiling

point elevation are the same phenomenon.
The only differences are the mechanism, and the size of
the effect which is reflected in the sizes of the
constants, Kf & Kb.

The effects are easily seen in a phase diagram

Boiling Point Elevation

What is the normal boiling point of a 2.50 m glucose,
C6H12O6, solution?

Freezing Point
Depression
Calculate the freezing point of a solution that contains 8.50 g of benzoic acid
(C6H5COOH, MW = 122) in 75.0 g of benzene, C6H6.

Determination of Molecular
Weight by Freezing Point
Depression

The size of the freezing point depression depends on two

things:
1. The size of the Kf for a given solvent, which are well
known.
2. And the molal concentration of the solution which
depends on the number of moles of solute and the kg of
solvent.

If Kf and kg of solvent are known, as is often the case in

an experiment, then we can determine # of moles of solute
and use it to determine the molecular weight.

Determination of Molecular
Weight by Freezing Point
A 37.0 g sample of a Depression
new covalent compound, a nonelectrolyte, was dissolved
in 2.00 x 102 g of water. The resulting solution froze at -5.58 oC. What is the
molecular weight of the compound?

Osmotic Pressure

When a solution and a pure solvent are separated by a

semipermeable membrane, a barrier that allows solvent
molecules but not solute molecules to pass through, the flow of
solvent in opposing directions is unequal and produces an
osmotic pressure, which is the difference in pressure between
the two sides of the membrane.
Because of the large
magnitude of osmotic
pressures, osmosis is
important in biochemistry,
biology, and medicine; every
barrier that separates an
organism or cell from its
environment acts like a
semipermeable
Examples of semipermeable
membranes include:
membrane,
1. permitting
cellophane andthe
saran flow
wrap of water
2.
skin
but
solutes.
3.
cellnot
membranes
4.
5.

Dialysis uses a semipermeable membrane.

Preserving fruits and meats employing cell membranes and using salt prevents
bacterial growth.

Osmotic Pressure
Osmosis is the net flow of solvent through a
membrane due to different solute concentrations; the
direction of net solvent flow is always from higher
solvent concentration to lower solvent concentration or
from the side with the lower concentration of solute to
the side with the higher solute concentration.
Osmosis is a rate controlled phenomenon. The flow
from high to low solvent is faster than low to high
solvent concentration until equilibrium is reached.
Osmotic pressure () of a solution depends on the
concentration of dissolved solute particles:

Osmotic Pressure

Osmotic pressures can be very large.

For example, a 1 M sugar solution has an osmotic pressure of
22.4 atm or 330 p.s.i.

Since this is a large effect, the osmotic pressure measurements

can be used to determine the molar masses of very large
molecules such as:
1. Polymers
2. Biomolecules like
proteins
ribonucleotides

Osmotic Pressure
A 1.00 g sample of a biological material was dissolved
in enough water to give 1.00 x 102 mL of solution. The
osmotic pressure of the solution was 2.80 torr at 25oC.
Calculate the molarity and approximate molecular
weight of the material.

Solutions of Solids
Solutions are not limited to gases and liquids; solid solutions also
exist.
Amalgams, which are usually solids, are solutions of metals in
liquid mercury.
Network solids are insoluble in all solvents with which they do
not react chemically; covalent bonds that hold the network
together are too strong to be broken and are much stronger than
any combination of intermolecular interactions that might occur
in solution.
Most metals are insoluble in all solvents but do react with
solutions such as aqueous acid or base to produce a solution; in
these cases the metal undergoes a chemical transformation that
cannot be reversed by removing the solvent.

Aggregate Particles in
Aqueous
Solution
A mixture of gases is the only combination of
substances that cannot produce a suspension or colloid
because their particles are small and form true
solutions

A colloid can be classified as:

1. a sol or gel, a dispersion of solid particles in a liquid or
solid in which all the solvent has been absorbed by the solid
particles, thus preventing the mixture from flowing readily;
2. An aerosol, a dispersion of solid or liquid particles in a gas;
3. An emulsion, a dispersion of one liquid phase in another
liquid with which it is immiscible.

Interactions in Liquid
Solutions

All common organic liquids, whether polar or not, are miscible; the
strengths of the intermolecular attractions are comparable, the
enthalpy of solution is small, and the increase in entropy drives the
formation of a solution.
If predominant intermolecular interactions in two liquids are very
different from one another, they may be immiscible, and when
shaken with water, they form separate phases or layers separated by
an interface.
Only the three lightest alcohols are completely miscible with
water; as the molecular mass of the alcohol increases, so does the
proportion of hydrocarbon in the molecule, which leads to fewer
favorable electrostatic interactions with water

Emulsions

Emulsions are colloids formed by the dispersion of

a hydrophobic liquid in water, thereby bringing two
mutually insoluble liquids in close contact.

Various agents have been developed to stabilize

emulsions, the most successful being molecules that
combine a relatively long hydrophobic tail with a
hydrophilic head. Examples of emulsifying agents
include soaps and detergents.
Micelles

Micelles

In the absence of a dispersed hydrophobic liquid phase,

solutions of detergents in water form organized spherical
or cylindrical aggregates called micelles, which minimize
contact between the hydrophobic tails and water.
In a micelle, only the hydrophilic heads are in direct
with water,
the
hydrophobic
are inthat
the
contact
Phospholipids
aand
large
class
of biologicaltails
molecules
consistof
ofthe
detergent-like
interior
aggregate.molecules that contain a hydrophilic
head and two hydrophobic tails; additional tail results in a
cylindrical shape that prevents phospholipids from forming a
spherical micelle
Cells
are collections of molecules that are surrounded by a