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Segment 1: Lesson 1Slide 1

Heating
(Review Ch. 9)
The heat required to heat an object is proportional to:
Mass of the sample (m)
Heat for one gram for 1 degree (Specific Heat Capacity)
Temperature change required. (T)
q = (m)(S.H.)(T)
The product, mass times specific heat is the heat capacity. cp
q = cp T (calorimetry)
When a hot sample is in contact with a colder one, the heat gained
by the colder sample must equal the heat lost by the hot sample.
The heat required to vaporize one mole of a liquid is its molar
heat of vaporization. Hvap
The heat removed when one mole of a liquid is frozen is the molar
heat of fusion.
Hfusion
The heat to absorbed when a mole of solid passes directly from the
solid into to the gas phase is called the molar heat of sublimation.
Hsub

Segment 1: Lesson 1Slide 2


Heating Problems
1. A system (Cp = 20.8 J/ oC) was heated at a constant 1 atm
pressure from 25 oC to 50 oC. If the volume increased from
24.4 L to 26.5 L, calculate: q, w, E, and H
Solution:
q = Cp T = (20.8 J/ oC) (50-25) oC = + 520 J (Sign?)
Since heating was at constant pressure, q = H H = +520 J
w = -P V = - (1 atm)(26.5 - 24.4) L = -2.1 L atm= - 213 J(sign?)
H = E + (PV)
+520 J = E + (1atm)(26.5-24.4)L
+520 J = E + 213 J
E = +307 J

(sign?)
Is the comparison between H and E correct?
(Should more heat be required at constant pressure?)

Segment 1: Lesson 1Slide 3


Heating Problems
2. How much heat is needed to heat 150 g of Fe
(SH = 0.45 J/g oC) from 0.00 oC to 300 K?
Solution:
q = m x SH x T = (150 g)(0.45 J/ g oC) (26.85 - 0.00) oC
q = 1810 J---SIGN?
3. What will be the final temperature if 50.0 g of Fe at 100 oC is dropped
into 150 g of water (SH = 4.18 J / g oC) at 0.00 OC?
Solution:
Heat lost = Heat gained
(50.0 g)(0.45 J / g oC)(100 - T) = (150 g)(4.18 J/ g oC)(T - 0.00)
2250 - 22.5 T = 627 T - 0.00
649.5 T = 2250
checkpoint
T = 3.46 oC (LOGICAL?)

Segment 1: Lesson 2Slide 4


INTERMOLECULAR FORCES
(Chapter 6)

ALL particles: atoms, ions, and molecules attract each


other due to LONDON DISPERSION FORCE.

LONDON DISPERSION FORCE INCREASES WITH:


1. Molecular weight of the molecule
2. Volume of the molecule
3. Number of electrons in the molecule
4. Distance of electrons from nuclei.

Segment 1: Lesson 2Slide 5


INTERMOLECULAR FORCES

LONDON DISPERSION FORCE IS CAUSED BY:


1. Electrons move much faster than nuclei and try
to avoid other electrons on nearby molecules.
2. Electrons on the side of a molecule that is
adjacent to another molecule will cause the
electrons of the adjacent molecule to move away.
3. As electrons of the second molecule move away,
positive charge is exposed causing an attraction
for the electrons of the first molecule.
4. Electrons of both molecules continue to oscillate
in phase resulting in a permanent attraction between
the two molecules.

Segment 1: Lesson 3Slide 6


(non covalent interactions)
Molecular Polarity

Polar molecules attract ions and each other.


1. Polar molecules must contain bonds between atoms that
have different electronegativities.
2. Polar molecules must have polar bonds that are arranged
unsymmetrically.
Polar molecules will have a dipole moment.
1. If a molecule is polar, the center of the positive charge
(from nuclei) and the center of the negative charge
(from electrons) will be separated by a distance r.
2. The dipole moment, , is the product of the charge
separated, Q, and the distance of separation, r. (=Qr)

Segment 1: Lesson 4Slide 7


INTERMOLECULAR FORCES

HYDROGEN BONDING IS THE ATTRACTION OF


A HYDROGEN ATOM ATTACHED TO A VERY
ELECTRONEGATIVE ATOM ON ONE MOLECULE
FOR A PAIR OF ELECTRONS ON AN ATOM OF
AN ADJACENT MOLECULE.
1. The hydrogen atom must be attached to F, O, or N
(the three most electronegative atoms.)
2. Any atom of an adjacent molecule that has a lone
pair of electrons can complete the hydrogen bond.
3. The hydrogen atom bridges the two molecules.
4. The hydrogen bridge is linear (180o)

Segment 1: Lesson 4Slide 8


INTERMOLECULAR FORCES

HYDROGEN BONDING (BRIDGING) IS THE


STRONGEST INTERMOLECULAR FORCE.
IF PRESENT AT ALL!!
1. Each hydrogen bridge is much weaker than a single
covalent bond.
2. However, a mole of hydrogen bonds can amount to
TENS of kJ.
3. The hydrogen bonding in water is extremely strong.
The energy of 2.5 atomic bombs is required to
vaporize 1 inch of water over a 1 square mile area!!!
Paper

Segment 1: Lesson 4Slide 9


INTERMOLECULAR FORCES
PROBLEMS
1. List all the types of INTERMOLECULAR FORCES that
exist between molecules of:
Cl2 CHCl3 PH3 AsH3 SbH3 HCF3 CH3OCH3 CH3CN
CH3NH2 ONF

CH3CH2CF3 CH3NHCH3

CH3COCH3

2. Arrange the 2 hydrogen bonded molecules order of LDF.


3. Arrange the 9 non hydrogen bonded molecules in order of LDF.
4. Arrange the 2 non-polar molecules in order of LDF.
checkpoint

Segment 1: Lesson 5Slide 10


SPONTANEITY OF SOLUTIONS
(Chatper 12 pgs 506-516)

Natural processes are favored by:


(DRIVING FORCES FOR SPONTANEOUS CHANGE)

1. An INCREASE in randomness (DISORDER)

2. An INCREASE in the amount of matter on which


ENERGY is distributed.

Segment 1: Lesson 5Slide 11


SPONTANEITY OF SOLUTIONS
(Chatper 12 pgs 506-516)

SPONTANEOUS MIXING (MISCIBILITY)


1. The environment of a molecule in the solution should be
similar to the environment it was in before mixing.
2. The intermolecular forces between solute and solvent
molecules should be similar to those between molecules
in the pure solvent and those between pure solute molecules.
3. The act of mixing generates disorder and favors forming
a solution.
4. Strong attraction between solute and solvent molecules
liberates energy and favors forming a solution.

SPONTANEOUS MIXING
Miscibility

IMF
IMF

If IMF = IMF
Remove partition

SPONTANEOUS MIXING
Miscibility

SPONTANEOUS MIXING
Miscibility

SPONTANEOUS MIXING
Miscibility
Random location for all particles
Miscible

Each particle experiences same force regardless of


type of particle near it.

Segment 1: Lesson 5Slide 16


INTERMOLECULAR FORCES

PROBLEMS:
1. Place the following under H2O or CCl4 indicating which of
solvent you think the following is soluble.
NaCl CH3OH

CH3OCH3

H2O
NaCl
CH3OH
SO2
HCl

SO2

Br2

HCl

CCl4
CH3OCH3
Br2

Segment 1: Lesson 6Slide 17


BULK PROPERTIES AND IMF
(pgs 470-478)

The equilibrium VAPOR PRESSURE of a liquid is the pressure


in a sealed container when the rate at which molecules escape the
liquid surface is the same as the rate at which they return.
1. RECALL: The average kinetic energy of a collection of
molecules is fixed by the temperature. (KE = 3/2 RT)
2. At any temperature, there is a distribution of molecular
energies. (BOLTZMAN DISTRIBUTION)
3. At any temperature, there is a fraction of molecules with a
kinetic energy greater than that needed to escape the surface.
4. These molecules escape into the gas phase and create the
vapor pressure.

Segment 1: Lesson 6Slide 18


BULK PROPERTIES AND IMF
The vapor pressure of a liquid increases with temperature.
the mathematical relationship is:
Hvap 1
run
lnP = a
R
T
rise
lnP
A plot of ln P vs 1/T should be linear
with a slope of -Hvap/R

( )

1/T
Or ln(P2/P1) = - Hvap /R (1/T2 - 1/T1)

Slope = rise
run

Segment 1: Lesson 6Slide 19


BULK PROPERTIES AND IMF
Problem: The heat of vaporization of water is 40.65 kJ/mol
and the vapor pressure of water is 92.6 Torr at 50 oC.
Calculate the expected boiling point of water.
SOLUTION:
The vapor pressure is 760 torr at the boiling point.
And 50 oC = 323.15 K.
ln(760/92.6) = - 40.65 x 103/8.314 (1/T2 - 1/323.15)
2.105 = - 4889.34(1/T2 - 0.0030945)
-4.3053 x 10-4 + 0.0030945 = 1/T2
0.002664 = 1/T2
checkpoint
T2 = 375.37 K = 102.2 oC

Segment 1: Lesson 6Slide 20


BULK PROPERTIES AND IMF

VAPOR PRESSURE
1. If the intermolecular force is HIGH, few molecules can
escape the liquid surface and the vapor pressure is LOW.
2. INCREASING the temperature increases the fraction
of the molecules that can escape and INCREASES
vapor pressure.
3. The BOILING POINT is the temperature at which the
vapor pressure is equal to the applied pressure. (at the
NORMAL boiling point, the vapor pressure is 1.00 atm.)
4. At the melting point, the solid and the liquid have the
same vapor pressure.
checkpoint

Segment 1: Lesson 6Slide 21


BULK PROPERTIES AND IMF
(pgs 254-256)

A PHASE DIAGRAM is a plot of pressure (Y-axis) vs.


Temperature (X-axis) showing the pressure at which two
phases coexist at any given temperature.
1. The solid, liquid and gas phases
are open areas on the diagram.
2. Lines represent the temperature
and pressure where two phases
exist in equilibrium.
3. The Critical point is the end
point of the liquid-vapor line.
4. At the triple point all three
phases are in equilibrium.

Segment 1: Lesson 6Slide 22


BULK PROPERTIES AND IMF
5

p
r
e
s
s
u
r
e

Liquid
1 atm

Solid

4
3

2
Gas
PROBLEMS:
1
Refer this phase diagram:
Temperature
1. What is the composition at each of the points numbered:
1, 2, 3, 4, 5, 6, 7, 8, 9.
2. Describe what occurs in moving from point 1 to point
5 and from point 6 to point 9.
3. Identify the: Critical point, Triple point,
checkpoint
Supercritical fluid region.

Segment 1: Lesson 7Slide 23


CRYSTALLINE SOLIDS
(Chapter 18)

CRYSTALLINE SOLIDS have an ordered, 3-dimensional


arrangement of particles. Amorphous solids have a
random arrangement of particles.
1. The array of points representing the location of particles
in crystalline solids is called the CRYSTAL LATTICE.
2. The smallest repeating unit of a crystal lattice is called
the UNIT CELL.
A. The unit cell has the same density as the bulk sample.
B. The unit cell has the same ratio of atoms (formula) as
the bulk sample.
C. Only 14 crystal lattices can exist and only 3 of them
are cubic unit cells (same length, width, and height.)

Segment 1: Lesson 7Slide 24


CRYSTALLINE SOLIDS

SIMPLE CUBIC UNIT CELL


1. Particles are located at the 8 corners of a cube.
2. Each of the 8 corners is shared by 8 unit cells.
3. Each unit cell has only one particle in it.
4. Since a particle is located at each corner of the unit cell,
the edge length of the unit cell is twice the radius of the
particles.
l = 2r
5. The density of the unit cell (mass / volume) is:
Density = (1 x atomic wt./ 6.02 x 1023)
l3

Segment 1: Lesson 7Slide 25


CRYSTALLINE SOLIDS

BODY-CENTERED CUBIC UNIT CELL


1. Particles are located at the 8 corners and at the center
of the unit cell.
2. The corners again contribute 1 particle to the unit cell
and the one in the center contributes another one.
3. Particles touch across the diagonal from the front-top-left
to the back-bottom-right. There are four radii across
this length.
3 l = 4r
4. The density (mass / volume) is:
Density = (2 x atomic wt./ 6.02 x 1023)
l3

Segment 1: Lesson 7Slide 26


CRYSTALLINE SOLIDS F

FACE-CENTERED UNIT CELL


1. The 8 corners again contribute one particle to the unit cell
and each of the 6 face contribute a particle to each of
two unit cells. The total particles per unit cell is 4.
2. Particles touch each other across the diagonal of each
face of the unit cell. This distance spans 4 radii.
2 l = 4r
3. The density (mass / volume) is:
Density = (4 x atomic wt./ 6.02 x 1023)
l3

PROBLEMS:
4. Copper forms a face-centered cubic unit cell with an
edge length of 361 pm. What is the radius of the
copper atom? What is the density of copper?
Body Centered Cubic Lattice
Radius:

2 L = 4R

(1.414)(361 pm)
R=
4

4 (At.Wt.)
6.02 x 1023
Density =
L3
Density =

R = 128 pm

2
10
cm
L = 361 x 10 m
1m
L = 3.61 x 10-8 cm

(4)(63.54)
(6.02 x 1023)(3.61 x 10-8)3

-12

= 8.97 g/cm3
checkpoint

Equilibrium Vapor Pressure


Energy Input

Rate of
escape

Gas molecules
EQUALS

Rate of
return

Boltzman Distribution of Energy


Most Probable Energy
Average Energy
Vaproization Energy
N(E)

Molecules with enough


energy to escape and
cause vapor pressure
Energy(E)

Simple Cubic Crystal Lattice


Each particle included
in 8 unit cells (1/8)
4
1
R

3
2

8 corners(patticles)
Unit Cell
1/8 x 8 = 1 particle
(1) At.Wt.
L
per unit cell
6.02 x 1023
Density
=
m/V=
Length of unit cell(L) = 2R
L3 (2R)3

Face Centered Cubic Lattice


All 6 faces are identical
Each corner only front face is shown
particle in 8
Each face particle
unit cells
shared in two
2 L = 1234 R
unit cells.
L
L
Six faces
contribute 3
L
particles
Eight
4 (At.Wt.)
Particles touch each
6.02 x 1023
corners
other across diagonal Density =
contribute
L3
L
1 particle
Total particles per unit cell = 4

Body Centered Cubic Lattice

Number of particles per unit cell = (8 x 1/8 + 1)


2 Particles per unit cell

Body Centered Cubic Lattice

Body Centered Cubic Lattice

Body Centered Cubic Lattice

3L

2L
3L =4R
Density =

2 x Atomic Mass
6.02 x 1023
L3

Phase Diagrams
5

p
r
e
s
s
u
r
e

Liquid
1 atm

Solid

3
2

Gas

Temperature

HYDROGEN BONDING
(BRIDGING)
Hydrogen bonded to an atom
with same electronegaivity:

X
180o

Hydrogen bonded to O, N or F:
Adjacent atom with lone pair:
X

+
Attraction

Pair of electrons

LONDON DISPERSION FORCE

SINGLE MOLECULE

+
+

ADJACENT MOLECULE
Attr.

ELECTRONEGATIVITY
INCREASE:
1.0 1.5
Li

2.1
H
2.0 2.5

Be

3.0

C
P

OBSERVATION:
When comparing atoms on different rows
on the periodic table, the element closest
to the noble gas on its row will have
the higher electronegativity.

3.5 4.0
N

O
Cl
Br
I

INCREASE:

DIPOLE MOMENTS
Spherical electron distribution
No charge separation

r = 0 and = 0
Center of negative charge

Center of positive charge


Charges separated
=qxr

Polarity and shape of molecules


Carbonate, CO32-, is NOT polar but contains polar bonds,
The bond dipole moments are in
2
O
symmetrically arranged because
all angles are 120o. The bond dipole
C
moments all cancel, resulting
O
O
in no dipole moment for the ion .
Nitrite, NO21-,IS polar because polar bond dipole moments dont cancel.
Bond dipole moments are not
1
O
symmetrical and add to produce
a net dipole moment through the
N
nitrogen atom bisecting the
O
ONO angle.

UNSYMMETRICAL
MOLECULES

VSEPR:
(m+n)
2. AX2

Symmetrical(S) AXE Nonsymmetrical(N)

3. AX3

4. AX4

5. AX5

AX2E (N)
AX3E (N)
AX4E (N)

AXE2(N)
AX2E2 (N) AXE3 (N)

AX3E2 (N) AX2E3 (S)

AXE4 (N)

6. AX6 S AX5E (N) AX4E2 (S) AX3E3 (N) AX2E4 (S) AXE5 (N)
EXAMPLE: SF3- anion Valence electrons = 6 + 3 x7 +1 = 28
3
2
SF3- anion is Non symmetrical
8 28
2 4
VSEPR = A X3 E 2 and POLAR.
24
4

Hydrogen Bonding (Bridging)


This is a H-Bond
O---H O angle is 180o
H

O ----- H

H
This is a H-O covalent bond

N
H

These are H-Bonds


H
N

H
H

Hydrogen Bonding (Bridging)

Segment 1Check point #1


Your two problems for 2 points.
1. Given that 23.6 kJ of hear are required to completely vaporize
60.0 g of benzene, (C6H6(l)) at 80.1 oC, calculate the molar
Enthalpy of vaporization of benzene.
2. A 50.0 g sample of Cu (Cp = 24.4 J/mol/oC) at 98.6 oC
is dropped into 125 g of water (Cp = 75.3 J/mol/oC) at 25.3 oC.
What is the final temperature of the Cu and water?

return

Segment 1Check point #2


Your 4 Problems:

Consider the molecules below:


NCl3 PCl3 PCl5 HCF3 HNCl2
1. Which two molecule(s) are not polar?
2. Which molecule(s) have hydrogen bonding?
3. Which molecule has the most polar BOND?
4. Which molecule has the highest London Force?

5 parts

return

Segment 1Check Point #3


Your Problem for 1 point
Problem: The heat of vaporization of water is 40.65 kJ/mol
and the vapor pressure of water is 92.6 Torr at 50 oC.
Calculate the vapor pressure of water at 25.0 oC.

NOTE: The measured vapor pressure of water at 25oC is 23.8 Torr


return

Segment 1Check Point #4


Your problem:
Draw the Lewis bonding structure for CH4O, CH3CN, and CH3F
Rank each molecule according to the criteria on each column
In the table below: Use ranking 1,2,3 for largest to smallest.
(0 if the molecule does not have the property to be ranked.)
H-bonding

London Dispersion

Most polar bond

boiling point

CH4O
CH3CN
CH3F
15 parts

return

Segment 1Check Point #5


Your 2 problems:

P(atm)

Consider this phase diagram:

1.0
1

ab
T(oC)

cd

1. What do points a, b, c, d represent?


2. What phase changes occur in going along the arrow from
point 1 to point 2?
return

7 points

Segment 1Point #6
Your problem:
Platinum (at. mass = 195.08) has a density of 21.45 g/cm3
and forms a face centered cubic crystal. What is the diameter of
the platinum atom?

1 part