1

CHE
102/112/114

Dr. Stacey Gulde

Take out your Syllabus & your
Chapter 13 Outline

Pg. 1
REGISTRATION
Registration Procedure:
If you are not completely registered for lecture and recitation/lab, see Mrs. Clarke in NSC 266 or Dr. Valerie Frerichs in
NSC 344.
Important Dates:
Saturday, January 19, 2013: Last day to drop a course.
Tuesday, January 22, 2013: Last day to add a course
Friday, March 29, 2013: Last day to resign a spring 2013 course with a grade of R (by 11pm).
Monday, April 29, 2013: Last lecture day.
Thursday, May 02, 2013: Final Exam period starts.
3
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Ti30X IIS
Ti30XA
4
Lecture
It is in your best interest if you read text in advance
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Schedule has chapters covered each week

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Bring to EVERY class
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Homework:
Mastering Chemistry
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Homework:
Mastering Chemistry
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Optional Assignments:
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7
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CHE114 students will get an e-mail w/Recitation Rm #
Laboratory Notes on UB Learns give all Pre-& Post Lab
questions!!


Lab
8
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Mastering Chemistry
Pg. 3
Final exam: Saturday May 17
th
@ 8am
Pg. 7 Tentative
Schedule
Week of Monday Tuesday Wednesday Thursday Friday Saturday
Jan. 27
Ch. 13
Classes Start
No Rec/Lab
No Rec/Lab No Rec/Lab No Rec/Lab No Rec/Lab No Rec/Lab
Feb. 03
Ch.13&14
Rec Only
(Last day to
Add/Drop)
Rec Only
Rec Only
Hw(Intro)
Rec Only
Rec/Check In/Lab
Safety Test
Rec/Check In/
Lab Safety Test
Feb. 10
Ch. 14
Rec/Check In/
Lab Safety Test
Hw 13
Rec/Check In/
Lab Safety Test
Rec/Check In/
Lab Safety Test
Rec/Check In/
Lab Safety Test
Exp.13 Exp.13
Feb. 17
Ch. 15
Quiz 1
Exp.13
Hw14
Exp.13 Exp.13 Exp.13 Exp.14 Exp.14
Feb. 24
Ch. 16
Exp. 14
Hw15
Exp.14 Exp.14 Exp.14 Exp. 15 Exp. 15
Mar. 03
Ch. 16&17
Exp. 15 Exp. 15 Exp. 15 Exp. 15
Exp. 17;
EXAM 1
Exp. 17
Mar. 10
Ch. 17
Exp. 17
Hw16
Exp. 17 Exp. 17 Exp. 17 Exp. 18 Exp. 18
Mar. 17
Mar. 24
Ch. 19
Exp. 18
Hw17
Exp. 18 Exp. 18 Exp. 18 Exp. 19 Exp. 19
Mar. 31
Ch. 20
Quiz 2
Exp. 19
Hw19
Exp. 19 Exp. 19 Exp. 19 Exp. 22-Known
Exp. 22-
Known
Apr. 07
Ch. 20
Exp. 22-
Known
Hw20A
Exp. 22-
Known
Exp. 22-
Known
Exp. 22-
Known
Exp. 22-
Unknown;
EXAM 2
Exp. 22-
Unknown
Apr. 14
Ch. 21
Exp. 22-
Unknown
Exp. 22-
Unknown
Exp. 22-
Unknown
Exp. 22-
Unknown
Good Friday,
No Rec/Lab;
Last day to Resign
Hw20B
No Rec/Lab
Apr. 21
Ch. 21&23
Exp. 23A Exp. 23A Exp. 23A Exp. 23A Exp. 23A Exp. 23A
Apr. 28
Ch. 23
Quiz 3
Exp. 23B/C
Hw21
Exp. 23B/C Exp. 23B/C Exp. 23B/C Exp. 23B/C
Exp. 23B/C
Lab
Checkout
May 5
Ch. 18
Lab
Checkout
Hw23
Lab
Checkout
Lab
Checkout
Lab
Checkout
Lab Checkout
Last Day Classes
Hw18?
Reading Day
May 12
Final Exam
8:00AM
SPRING RECESS
CHE 102/112 Exam1-Friday, Febuary 28, 2014 - 5:00PM
CHE 102/112 Exam2-Friday, April 11, 2014 - 6:00PM
Pg. 4
Pg. 5
A Very Tentative
schedule:


Chapter Topic(s)
13 Solution chemistry
14 Kinetics
15 Equilibrium
16 Acids and bases
17 Other aqueous equilibria
Spring Break
19 Thermodynamics
20 Electrochemistry
21 Nuclear Chemistry
23 Transition Metals & Coordination Chemistry
18 Environmental chemistry
Pg. 5
Getting Help
Go to Instructor office hrs: Starts 1/27
See pg 1 of syllabus

Go to NSC110 for TA help: Starts 2/10
1
st
come, 1
st
serve basis
11am 1pm busiest time of day

We expect you to try problems before asking questions, show us your work
and how far youve gotten in the problem, BRING YOUR BOOK
You should expect to get correct help in timely & courteous manner
If not TELL an instructor! Give day & time of incident
13
Chapter 13:
Properties of
Solutions
Suggested review:
Chap 4 (Concentration of solutions)
Chap 11 (11.1 11.5)

Skip section 13.6

14
Solutions
Solutions are homogeneous (uniform) mixtures
Solute usually present in smaller amounts, its dissolving
Solvent usually present in larger amounts, causes
dissolving
Usually water but not always
15
Dynamic Equilibrium
Dissolution (dissolves) solute breaks apart
(usually into ions)

Crystallize - when dissolved solute
comes out of soln

Dynamic Equilibrium when the rates
of these processes are equal
16
dissolve
crystallize
Types of Solutions
1. Saturated solutions contains max amount of
solute for a solvent, at a specific temp
Sugar: 25C = 211g/100g H
2
O
50 C = 260g/100g H
2
O

If add more solute, it wont dissolve
Solubility amount of solute needed to form a
saturated solution
2. Unsaturated solutions contains less than the
max amount of solute, at a specific temp
If add more solute, it will dissolve

17
Types of Solutions
3. Supersaturated solutions contains more than
the max amount of solute, at a specific temp
To make: heat saturated soln, add solute then cool to
original temp
Not stable
If add more solute, it crystallizes
18
Link:
NaC
2
H
3
O
2
Why do Solutions form?
Existing forces & bonds are broken then new ones
created

Intermolecular forces
(IMF)
Chap. 11
Intra
Types of IMF
Why do Solutions form?
Solvation when ions or molecules are
surrounded by solvent molecules in a specific way
Hydration special case b/c water is the solvent

20
NaCl in water Water orients
to NaCl
Water pulls
NaCl apart
NaCl

Movie
Na
+
Cl
-
A Closer Look at
NaCl in Water

1. Must break solute-solute attraction (Ionic bond)
Breaking requires energy, endothermic


2. Must break solvent-solvent attraction (IMF: H-bonds)
Breaking requires energy, endothermic


3. Must form IMF solute-solvent interactions
(Solvation/Hydration)
Forming gives off energy, exothermic
Interactions increase: w/inc. _______& dec. _____ size
NaCl (s) Na
+

(aq) + Cl
-
(aq)
charge ion
Why do Solutions form?
Each step is associated with an energy change (AH)


AH
soln
can be
endothermic (+)
or exothermic (-)
Depends on size of IMF


Soln formation will always occur when AH
soln
(-)
Solute-solvent particles are attracted to each other,
they want to be together
22
3 2 1 soln
H H H H A + A + A = A
Why do Solutions form
if H
soln
> 0
Ex: NH
4
NO
3
in H
2
O, AH
soln
= +26 kJ/mol, Endothermic

Solution formation is favored by an
increase in disorder (randomness)
Aka: Entropy!! (AS)

Spontaneous happens automatically
No input of energy

Ex: NH
4
NO
3
forms a soln

- Enthalpy (AH) : disfavored
- Entropy (AS) : favored
23
Entropically
disfavored
Entropically
favored
Why do Solutions form?
Review
1. Enthalpy (AH):
Solutions always form when AH
soln
< 0 (exo)
Strong solvent-solute interactions

2. Entropy (AS):
Increased disorder
Helps compensate for AH
soln
> 0 (endo)
24
Factors Affecting Solubility
1. Solute-Solvent Interactions:
Substances likely to dissolve if they have similar forces

LIKE dissolves LIKE!
Polar solvents dissolve: polar or ionic solutes
Nonpolar solvents dissolve: nonpolar solutes

Liquid solubility terminology:
Miscible mixes completely
Immiscible doesnt mix significantly
- Ex: Oil (nonpolar hydrocarbon) & Water (polar)
25
Sample Problems
a) Is ethanol (C
2
H
6
O) miscible in water?



Dominate IMF involved:
Water =
Ethanol =
26
C
H
H
H C
H
H
O H
YES
H-bonding
H-bonding
Sample Problems
b) Is hexane (C
6
H
14
) miscible in water?
27
hexane
water
Factors Affecting Solubility
(in water)
Structural Factors: Like Dissolves Like

Solubility of liquids decrease
as carbon chain length
increase


Solubility of gases increase w/
Increased Mm
Increased polarity
28
28
28
32
40
84
Mm
(g/mol)
Factors Affecting Solubility
2. Pressure:
Strongly affects gasses in liquids, no effect on solids or
liquids in liquids
Gas solubility increases as the
pressure of the gas (partial pressure)
over the solvent increases

Henrys Law
29
g g
kP S =
S
g
= solubility of gas (M)
P
g
= partial pressure of gas above solution
k = Henrys law constant
(varies w/temp & solute-solvent pair)
Factors Affecting Solubility
3. Temperature:
A. Depends on phase:
As temperature increases:
a) Solubility of most solid solutes in water
increases


b) Solubility of most gas solutes in water
decreases
30
Factors Affecting Solubility
3. Temperature:
B. Depends on solution process:
Endothermic: Added heat overcomes solute-solute
Solubility increases w/increased temp
- Additional heat pushes for more soln to form


Exothermic: Added heat overcomes solute-solvent forces
Solubility decreases w/increased temp
- Additional heat counteracts more soln to form
31
A + B soln
A + B soln
HEAT +
+ HEAT
Concentration of Solutions
Qualitatively: relative term
Insoluble slightly soluble soluble very soluble


Dilute vs. concentrated
The more solute you have the more concentrated the soln
32
< 0.1g/100g
> 2g/100g
Concentration of Solutions
Quantitatively: numerically calculated
1. Mass percent, parts per million & parts per
billion
Units = None



33
solution of mass total
component of mass
component of % Mass =
solution of mass total
component of mass
(ppm) million per parts =
solution of mass total
component of mass
(ppb) billion per parts =
x 100
x 10
6

x 10
9

Sample Problem
Express the concentration of 1.0g glucose (C
6
H
12
O
6
) in
100.kg of water, in mass% & ppm

34
Mass%=
1.0g
100,001g
x100 = 0.0010%
ppm=
1.0g
100,001g
x10
6
= 10.ppm
solution of mass total
component of mass Soln =
100,000g
1.0g + 100,000g
Concentration of Solutions
2. Mole fraction, X:
Subscript indicates the component of interest
Units = none


Sample: 2.0 mols of glucose dissolved in 12 mols water
35
components all of moles total
A of moles
= X
A
= X
6 12 6
O H C
mol 2.0
mol 12 mol 2.0 +
0.14 =
Concentration of Solutions
3. Molarity, M: (Chap4)

Most widely used
Units = mol/L

Easy to measure volume, but it changes with temp
36
soln of L
solute of moles
= M
Concentration of Solutions
4. molality, m:
Units = mol/kg
Independent of temp

Must know density of soln to calculate molality
Also allows you to convert b/t M & m
37
solvent of kg
solute of moles
= m
Sample Problems
1. What is the m & M concentration of a dilute solution that has
1.00g glucose (C
6
H
12
O
6
) dissolved in 100.kg of water?
glucose: Mm = 180.16 g/mol
38
1.00g C
6
H
12
O
6

100.kg H
2
O
m =?
|
|
.
|

\
|
solvent kg
solute mol
1.00g C
6
H
12
O
6

|
.
|

\
|


180.16g C
6
H
12
O
6

1mol C
6
H
12
O
6

= 0.00555mol C
6
H
12
O
6

= m
0.00555mol C
6
H
12
O
6

100.kg H
2
O
kg
mol
x
5
10 55 . 5

=
(solute)
(solvent)
Sample Problems
1. What is the m & M concentration of a dilute solution that has
1.00g glucose (C
6
H
12
O
6
) dissolved in 100.kg of water?
glucose: Mm = 180.16 g/mol
39
1.00g C
6
H
12
O
6

100.kg H
2
O
M =?
|
.
|

\
|
soln L
solute mol
1.00g C
6
H
12
O
6

|
.
|

\
|


180.16g C
6
H
12
O
6

1mol C
6
H
12
O
6

= 0.00555mol C
6
H
12
O
6

100.kg H
2
O
|
.
|

\
|

1 mL
1.00g H
2
O
|
.
|

\
|
1000mL
1L
D
water
= M
0.00555mol C
6
H
12
O
6

100.L soln
L
mol
x
5
10 55 . 5

=
= 100. L H
2
O
(solute)
(solvent)
To get volume,
need Density
|
|
.
|

\
|
1kg
g 1000
V
solvent
= V
soln
Soln = 1g +100,000g =100,001g
Soln =100kg
Concentration of Solutions
NOTE:
If water is solvent: M & m are ~ equal for dilute solns
Ex: 1.0g glucose (C
6
H
12
O
6
) in 100.kg of water
(See above problem)

1 kg solvent ~ 1 kg solution

Density of water = 1.00 g/mL or 1.00kg/L
40
Sample Problems
2. A solution is prepared by adding 50.0g of glycerol, C
3
H
8
O
3
, to
60.0mL of water. The density of the solution is 1.10 g/mL.
Calculate the molality and molarity of the solution.
Glycerol: Mm = 92.11 g/mol
41
50.0g C
3
H
8
O
3

60.0mL H
2
O
D
soln
=1.10g/mL
m =?
|
|
.
|

\
|
solvent kg
solute mol
50.0g C
3
H
8
O
3

|
.
|

\
|


92.11g C
3
H
8
O
3

1mol C
3
H
8
O
3

= 0.543mol C
3
H
8
O
3

60.0mL H
2
O
|
.
|

\
|


1 mL
1.00g H
2
O
= 0.0600kg H
2
O
|
|
.
|

\
|
g 1000
1kg
D
water
= m
0.543mol C
3
H
8
O
3

0.0600kg H
2
O
kg
mol
05 . 9 =
= 60.0g H
2
O
(solute)
(solvent)
To get mass,
need Density
Do we use
1.10g/mL?
A. Yes
B. No
Sample Problems
2. A solution is prepared by adding 50.0g of glycerol, C
3
H
8
O
3
, to
60.0mL of water. The density of the solution is 1.10 g/mL.
Calculate the molality and molarity of the solution.
Glycerol: Mm = 92.11 g/mol
42
50.0g C
3
H
8
O
3

60.0mL H
2
O
D
soln
=1.10g/mL
110.0g Soln
|
.
|

\
|


1.10 g Soln
1 mL
= 0.100L Soln |
.
|

\
|
1000mL
1L
= M
0.543mol C
3
H
8
O
3

L
mol
43 . 5 =
50.0g =
Solvent Solute Soln + =
= 0.100L Soln
60.0g +
110.0g =
D
Soln
(solute)
(solvent)
M =?
|
.
|

\
|
soln L
solute mol
Does
V
solvent
=V
soln
?
A. Yes
B. No
Colligative Properties
Colligative property depends on quantity but
not the kind of particles (concentration important)

1. Vapor Pressure
2. Boiling Point
3. Freezing Point
4. Osmotic Pressure
43
Must consider what the solute dissolves into?
Non-Electrolytes: dissolve as entire molecules
Molecular compounds
Ex. Glucose: C
6
H
12
O
6
(s) C
6
H
12
O
6
(aq)

Strong Electrolytes: break up into many IONS
Ionic, Strong Acid or Strong Base
Al
2
(SO
4
)
3
(s)


vant Hoff factor, i:
compensates for # of
particles dissolved
ESTIMATIONS
44
2Al
3+
(aq) +3SO
4
2-
(aq)

water

water
Chemical
Particles
dissolved
(i)
Glucose:
C
6
H
12
O
6

1
NaCl 2
MgCl
2
3
FeCl
3
4
Al
2
(SO
4
)
3
5
Molecular
Ionic
1. Vapor Pressure
Lowering
Vapor pressure, VP pressure exerted by a vapor
at equilibrium
A high vapor pressure means many gas molecules present
Volatile exhibits VP (acetone)
Nonvolatile no VP (glycerin)

45
1. Vapor Pressure
Lowering
Adding a nonvolatile solute to a solvent ALWAYS
LOWERS the vapor pressure of the solvent

Solvent becomes more stabilized in liquid state, thus
producing fewer gas particles
46
1. Vapor Pressure
Lowering
Raoults Law:



P
soln
depends on the total conc. of solute
particles added
1mol CaCl
2
lowers VP more than 1mol NaCl
- CaCl
2
= ____ ions NaCl = ____ ions
Ideal solutions obey Raoults Law
Solute conc. is low
Solute & solvent have similar size & IMF
47
( )( )

=
solvent solvent soln
P X P
P
soln
= VP of solution (with
nonvolatile solute)
X
solvent
= mole fraction
P

solvent
= VP of pure solvent
0.0 0.2 0.4 0.6 0.8 1.0
S
o
l
u
t
i
o
n

v
a
p
o
r

p
r
e
s
s
u
r
e

(
P
s
o
l n
)
Mole fraction of solvent (X
Solvent
)
3 2
Sample Problem
Predict the vapor pressure of a solution prepared by
mixing 42.9g glycerin (C
3
H
8
O
3
) with 175g of water at
25C. The vapor pressure of pure water at 25C is 23.76
torr.
48
42.9g C
3
H
8
O
3

175g H
2
O
P
soln
=?
P
solvent
=23.76 torr
( )( )

=
solvent solvent soln
P X P
42.9g C
3
H
8
O
3

|
.
|

\
|


92.09 g C
3
H
8
O
3

1mol C
3
H
8
O
3

= 0.466 mol C
3
H
8
O
3

175g H
2
O
|
.
|

\
|


18.02g H
2
O
1mol H
2
O
= 9.71 mol H
2
O
Total = 10.18 mol
=
soln
P
|
|
.
|

\
|
9.71 mol
10.18 mol
( ) torr 23.76 = 22.7 torr
total
solvent
n
n
solvent
X =
2. Boiling point
Boiling point temp at which liquid
VP equals external (gas) pressure

What does curve look like for
aqueous solns?

Adding a nonvolatile solute to a
solvent increases (ELEVATES)
the boiling point relative to the
of a pure solvent
49
Soln.
Water
Aqueous Boil pt?
A. Increase
B. Decrease
C. Stay Same
3. Freezing Point
(Exp. 13!)
Freezing point = melting point
temp at which VP of solid equals
VP of liquid
Starts at the Triple point


What happens for aqueous solns?
Adding a nonvolatile solute to a solvent decreases the
freezing point relative to that of a pure solvent
HOW?
50
Solid
Liquid
Gas
51
Freezing point depression
AT
f
= iK
f
m
Boiling point elevation
AT
b
= iK
b
m
Comparing:
Phase Diagrams
Black = Pure solvent
Blue = Soln
Bp:
increased
Fp:
decreased
Shifted
down
i = # of solute particles dissolved
m = molality of solute (mol/kg solvent)

Careful with AT: (always want to be positive)
AT
f
= T
pure
T
soln

AT
b
= T
soln
T
pure


K
b
=molal boiling point elevation constant
K
f
=molal freezing point depression constant
Both are dependent
on solvent
52
m iK T
b b
= A
m iK T
f f
= A
Sample problem
Ethylene glycol [EG, CH
2
(OH)CH
2
(OH)] is a common car
antifreeze. It is water soluble and is a nonvolatile nonelectrolyte
(bp=197C, d=1.11kg/L). Calculate the freezing point of a
30.0% (by volume) solution.
53
m iK T
f f
= A
Solute=EG Solvent=water
30.0 L
70.0 L
solvent
solute mols
kg
m =
O H 0.0L 7
EG 30.0L
2
=
|
|
.
|

\
|
1L
1.11kg EG
|
|
.
|

\
|
1kg
1000 g
|
|
.
|

\
|
62.07g EG
1mol EG
|
|
.
|

\
|
1kg H
2
O
1L H
2
O
= 7.66m
K
f
=
T
pure
=
( )( )( ) m T
m
C
f
66 . 7 86 . 1 1

= A = 14.2C
Soln Pure
T T T
f
= A
Bp=197C
d=1.11kg/L
14.2C = 0.0C T
soln

T
soln
= -14.2C
1.86C/m
i = 1
table
13.3
0.0C
4. Osmosis
Osmosis net movement of solvent molecules
across a semipermeable membrane
Semipermeable membrane allows passage
of certain small molecules (water)
but not large solute (molecules
or ions) due to tiny pores

Movement of solvent always occurs
from less solute more solute
As if to equalize the concentrations

Note: Bio uses high solvent low solvent
Pure H
2
O
Sugar Soln
Sugar conc.
decreases
after osmosis
(solute = 0) (solute > 0)
As solvent moves, liquid levels become unequal
resulting in different pressures
on each end of the tube




Osmotic pressure (t)
pressure required to stop
osmosis
Similar to ideal gas law
55
iMRT RT
V
n
i =
|
.
|

\
|
= t
t = Osmotic pressure (atm)
i = # solute particles in solution
V = volume (L)
R = ideal gas constant
(0.08206 Latm/molK)
T = temperature (K)
M = molarity of particles
(molecules or ions)
4. Osmosis
If osmotic pressures are equal for 2 solns, they are
called isotonic
Osmosis wont occur through a semipermeable membrane

Hypotonic soln of lower concentration
If place red blood cells in Hypotonic soln:
Hemolyisis water enters the cell = ruptures

Hypertonic soln of higher concentration
If place red blood cells in Hypertonic soln:
Crenation water leaves the cell = shrivel
56
Sample Problems
1. What is the osmotic pressure of a 0.010M aqueous
solution of CaCl
2
at 25C?
57
t = ?
M = 0.010 mol/L
T = 25C
iMRT =
Predicted i?
A. 1
B. 2
C. 3
D. 4
i = 3
(aq) 2Cl (aq) Ca (s) CaCl
2
2
+
+
( ) 3 =
( )
L
mol
010 . 0 ( ) K 298 ( )
K mol
atm L

08206 . 0
298K
0.74atm =
K mol
atm L
R

= 08206 . 0
Sample Problems
(try on your own)
2. The boiling point of ethanol (C
2
H
5
OH) is 78.4C & it has a boiling point
elevation constant of 1.22C/m. How many grams of glycerin (C
3
H
8
O
3
)
must be added to 200.0g of ethanol to produce a solution temp of 81.1C.
58
T = 78.4C
K
b
=1.22C/m

g
C3H8O3
= ?
( )( )( ) m K T
b b
i = A
Predicted i?
A. 1
B. 2
C. 3
D. 4
T
soln
= 81.1C
( ) 1
( )
m
C

22 . 1
( ) m
21 . 2 = m
g
C2H5OH
= 200.0g
AT
b
= T
soln
- T
Pure

= 81.1C - 78.4C
AT
b
= 2.70C
i = 1
= C

70 . 2
|
|
.
|

\
|
solvent kg
solute mol
(solute)
(solvent)
=
kg
mol 2.21

mols x
0.2000kg
kg 0.2000
3 8 3
O H C mols 0.422 x =
|
.
|

\
|


92.09g C
3
H
8
O
3

1mol C
3
H
8
O
3

= 40.7g C
3
H
8
O
3

Next slide
Chap. 13 Summary
Solution formation
1. Entropy increased disorder
2. Enthalpy favorable intermolecular interactions
Solubility
1. Influence of pressure Henrys Law
2. Influence of molecular structure like dissolves like
3. Influence of temperature
Concentration
1. Mass %, ppm, ppb
2. Mole fraction
3. Molarity
4. Molality
Colligative properties
1. Vapor Pressure Raoults Law
2. Boiling pt. elevation & Freezing pt. depression
3. Osmosis
4. vant Hoff factor, i
59
60