General Chemistry III

CH 223
Prof. Thomas Greenbowe
Knowledge of chemistry is fundamental
to understanding

medicine, engineering,
molecular biology, gene8cs,
ecology, material science,
atmospheric sciences, space
chemistry, geology, zoology,
botany, global climate change,

CH 223 Monday August 17, 2015 L01

Announcements:
Read Chapter 17 Sections 1-6 in Silberberg (skip 17.3 for now)
Connect HW#1A Due Thursday August 20, 11:58 p.m.
End of Chapter Problems on paper HW #1B: 17.15, 17.23, 17.34, 17.36,
17.51 Due Wednesday These problems form the basis of everything we
will do in the next three weeks. You must understand how to do these
problems.
Today:
Chapter 17 Sec8ons 1 -2 : Dynamic Equilibrium Systems, Equilibrium
Constant Expression, Keq ; Q
Tomorrow:
Chapter 17 Sec8ons 4 & 6 Compare Q to K & LeChateliers Principle
Equilibrium Calcula8ons (17.5) ICE Tables Sec8on 17.3 on Wednesday

CH 223 Monday August 17, 2015 L01

Announcements:
Connect on-line HW URL
hbp://connect.mheduca8on.com/class/u-general-chemistry-
summer-2015-ch223
On-line HW assignments found on this web site

 CH 223 is the third course in the 3-term General

Chemistry sequence.
Math 111 is a pre-requisite for CH 222
Math 112 is a pre-requisite for CH 223
Concurrent registration in the General Chemistry
Laboratory course, CH 229, is recommended but
not required.
CH223 meets MTWRF 9:00 am 10:50 am, Room
123 PAC

http://canvas.uoregon.edu

All course information is posted on Canvas
Syllabus **download the syllabus**
Announcements
Lecture schedule
Lecture notes, exam scores, and more

Required Course Materials

Textbook: Chemistry with ConnectPlus, Custom, by
Martin Silberberg; McGraw-Hill. Same textbook used in
CH221, CH222

Connect access code: comes with custom book, or

purchase on-line. ConnectPlus is not required.
i>Clicker

or i>Clicker 2

Register i-clicker through Canvas by tomorrow

approved non-graphing scientific calculator

Assessment
Using a weighted average
Hour exam 1, Wed. Aug. 26, 9:00 am 25%
Hour exam 2, Wed. Sept. 2, 9:00 am 25%
Final exam, Thurs. Sept. 11, 9:00 am 30%
Connect On-line homework

10%

Clicker questions

5%

In class activities/paper HW

5%

Mark the dates for the exams on your calendar now!

LearnSmart
LearnSmart is an adaptive learning system
designed to help you learn faster, study more
efficiently, and retain more knowledge for
greater success in this course.
LearnSmart focuses primarily on conceptual
understanding of the course material.
Homework assignments give you a chance to
apply your understanding to chemical
problems.

LearnSmart Prep Surveys

Brief assignments to prepare you for the days lecture.
Read the assigned sec8ons in the SmartBook rst.
LearnSmart focuses primarily on conceptual
understanding of the course material. (Homework
assignments give you a chance to apply your
understanding to chemical problems.)
If it works . . .

Access to Connect HW and LearnSmart

go directly to the Connect site for this course. The link
will be posted on Blackboard later today.

Greenbowe tgreenbo@uoregon.edu 177 Onyx

Office Hours:
Tuesdays: 11:00 11:50 p.m. 177 Onyx or 160E Klamath
Thursdays: 11:00 11:50 p.m. 177 Onyx or 160E Klamath
Or by appointment Or, drop in most afternoons

Course GTF
Brandon Schabes

Office Hours:
TBA

What do you need to know from CH222?

Concentra8on, molarity and solu8on calcula8ons,
gas laws, stoichiometry, equilibrium
Kine8cs: rates of reac8ons, rate laws
Lewis Structures for acids and bases
A + B -> C

Our Expecta8ons: Students will

Be prepared for class, arrive on 8me and not leave early, ask
ques(ons when you need help.
Respect fellow students and refrain from chalng, cell phone
use, outside reading, web surng, gaming and text messaging
during class.
One Minute Rule (10:49 am pack-up, not before, PLEASE!!)

Any questions about the syllabus, or

what to expect this term?

Gases in an Equilibrium State

The brown haze is a mixture of NOx gases

plus other gases.

Photochemical smog
Photochemical smog was rst described in the 1950s. It is the
chemical reac8on of sunlight, nitrogen oxides and vola8le organic
compounds in the atmosphere, which leaves airborne par8cles and
ground-level ozone. This noxious mixture of air pollutants can include
the following: Aldehydes, Nitrogen oxides (such as nitrogen dioxide)
Peroxyacyl nitrates, Tropospheric ozone, Vola8le organic compounds

How would you rate the air quality in

Eugene-Springeld area?
A.
B.
C.
D.

Excellent, healthy air except for a few days

Very good air. Only 30-60 days of stagnate air
Below average. 60 -120 days of poor air
Poor. Only between 30-60 days of acceptable air

Eugene/Springeld OR Lane county was ranked 5th in worst air

quality for 2006/2007 in the USA. Data from the
American Lung Associa8on site. Los Angeles was ranked no. 1.

Read more: hbp://www.city-data.com/forum/eugene-area/22262-pollu8on-eugene-
lane-county-springeld-oakridge.html#ixzz2xkhwoWsl

The NO2 concentra8ons in the air above Eugene are decreasing.

Why?

Read more: hbp://www.city-data.com/forum/eugene-area/22262-pollu8on-eugene-
lane-county-springeld-oakridge.html#ixzz2xkhwoWsl

i-Clickers
Are you ready for your rst clicker ques8on?
Clicker ques8ons (CQs) today will not count
Today we are tes8ng the clicker system
Some clicker ques8ons are to be done
individually (no talking with your neighbors).
We will tell you when a CQ is an individual
eort.
Todays clicker ques8ons are group ques8ons.
Talking with you neighbor is encouraged.

24

Introduce yourself to two other

students. Work as a group.

Colorless

Brown
H = +57.2 kJ

What do the double reac8on arrows

indicate in this reac8on?
A. The reac8on proceeds in both direc8ons
un8l [N2O4] equals [NO2] .
B. The reac8on proceeds in both direc8ons
un8l [N2O4] equals [NO2] .
C. The reac8on proceeds in both direc8ons
un8l there is no net change in [N2O4] and
[NO2] .
D. I dont know how to answer this ques8on.

Computer Anima8on

To run the anima8on:

You will need to use Firefox or Safari as a browser
You will need the Shockwave plug in.

hbp://group.chem.iastate.edu/Greenbowe/sec8ons/projecvolder/anima8ons/
no2n2o4equilV8.html

There are four concepts you need to observer in the anima8on.

Computer Anima8on

hbp://group.chem.iastate.edu/Greenbowe/sec8ons/projecvolder/anima8ons/
no2n2o4equilV8.html

Dynamic Equilibrium
Dynamic equilibrium is the condition wherein the rates of
the forward and reverse reactions are equal.
Once the reaction reaches equilibrium, the concentrations
of all the chemicals remain constant because the
chemicals are being consumed and produced at the
same rate.
A system at equilibrium does NOT mean equal amounts of
reactants and products.

What will happen to the color of the

gas when the temperature is lowered?
The intensity of the brown
color will

A. increase
B. decrease
C. stay the same
D. I dont know

H = +57.2 kJ

What will happen to the color of the

gas when the temperature is lowered?
The intensity of the brown
color will

A. increase
B. decrease
C. stay the same
D. I dont know

H = +57.2 kJ

What will happen to the color of the

gas when the temperature is lowered?

Small Quick8me Movie

hbp://chemed.chem.purdue.edu/demos/
main_pages/21.1.html

Cold

Warm

The Concept of Dynamic Equilibrium

Chemical equilibrium occurs when a reaction

and its reverse reaction proceed at the same rate.

Reaching equilibrium on the macroscopic and

molecular levels.

Demo: A Dynamic Equilibrium System

H = +57.2 kJ
Colorless when cold

Brown when warm

The Equilibrium State

All reactions are reversible and under suitable conditions
will reach a state of equilibrium.
At equilibrium, the concentrations of products and reactants
no longer change because the rates of the forward and
reverse reactions are equal.
At equilibrium: rateforward = ratereverse
Chemical equilibrium is a dynamic state because reactions
continue to occur, but because they occur at the same rate,
no net change is observed on the macroscopic level.
Reaction equations are written with a double arrow to indicate
that a state of equilibrium exists.

Table 16.7

Rate Laws for General Elementary Steps

Elementary Step

Molecularity

Rate Law

product

Unimolecular

Rate = k [A]

2A

product

Bimolecular

Rate = k[A]2

A+B

product

Bimolecular

Rate = k[A][B]

2A + B

product

Termolecular

Rate = k[A]2[B]

For elementary steps only, the reaction

coefficients become the exponents in the rate law.
This is because the elementary reactions tell us
about the actual collisions that take place.

An Equilibrium System
At equilibrium, both the forward and reverse
reactions occur at the same rate, we write
the equation with a double arrow to indicate
an equilibrium system:

N2O4(g)

2NO2(g)

Given the reaction as an elementary step:

N2O4(g) D 2NO2(g)
Write the rate laws for the forward and reverse
reactions.

N 2 O 4 2NO 2 : ratef = k f N 2 O 4
2NO 2 N 2 O 4 : rate r = kr NO 2
Where k = rate constant and [ ] indicates the
molar concentration.

At equilibrium, rate forward = rate reverse.

k f N 2 O 4 = kr NO 2

kf
kr

NO 2 eq
N 2 O 4 eq

Under these circumstances, the equilibrium constant

for the reversible reaction may be written as follows:
2

Kc =

NO 2 eq
N 2 O 4 eq

The Equilibrium Constant, Keq

The ratio of the rate constants is a constant
at that temperature, and the expression
becomes

Keq =

kf
[NO2]2
=
kr
[N2O4]

[NO2]2
Keq =
[N2O4]

Initial and Equilibrium Concentration Ratios for

the N2O4-NO2 System at 200C (473 K)

Initial
Expt

[N2O4]

[NO2]

Equilibrium
Q,

[NO2]2
[N2O4]

[N2O4]eq

[NO2]eq

Choose 0.0000
an experiment
0.1000
0.0000

0.00357

0.193

0.0000

0.000924

0.0982

0.0500

0.0500

0.0500

0.00204

0.146

0.0750

0.0250

0.0833

0.00277

0.170

Calculate
Keqs
0.1000

K = [NO2] eq
[N2O4]eq

Table 17.1

Initial and Equilibrium Concentration Ratios for

the N2O4-NO2 System at 200C (473 K)

Initial

Equilibrium

Expt

[N2O4]

[NO2]

Q, [NO2]2
[N2O4]

[N2O4]eq

[NO2]eq

K= [NO2] 2eq
[N2O4]eq

0.1000

0.0000

0.0000

0.00357

0.193

10.4

0.0000

0.1000

0.000924

0.0982

10.4

0.0500

0.0500

0.0500

0.00204

0.146

10.4

0.0750

0.0250

0.0833

0.00277

0.170

10.4

The Equilibrium Constant

Consider the generalized reaction
aA(aq) + bB(aq)

cC(aq) + dD(aq)

The equilibrium expression for this reac8on

would be

[C]c[D]d
Keq = a b
[A] [B]

If we start with N2O4(g) in a sealed bottle and raise the temperature:

Equilibrium

Keq and the extent of reaction

K reflects a particular ratio of product concentrations to
reactant concentrations for a reaction.
K therefore indicates the extent of a reac8on, i.e., how far a
reac8on proceeds towards the products at a given
temperature.
A small value for K indicates that the reaction yields little
product before reaching equilibrium. The reaction favors
the reactants.
A large value for K indicates that the reaction reaches
equilibrium with very little reactant remaining. The
reaction favors the products.

Which of the following best describes a reacWon at

equilibrium?
a) Reactants are being consumed and products
are being formed.
b) The rate of the reaction is zero.
c) The rate of the forward and reverse reactions
are equal.
d) Only products are present.
e) The rate of the forward reaction is greater than
the rate of the reverse reaction.

Which of the following best describes a reacWon at

equilibrium?
a) Reactants are being consumed and products
are being formed.
b) The rate of the reaction is zero.
c) The rate of the forward and reverse reactions
are equal.
d) Only products are present.
e) The rate of the forward reaction is greater than
the rate of the reverse reaction.

The Equilibrium Constant Expression

Consider the generalized reaction
aA(aq) + bB(aq)

cC(aq) + dD(aq)

Guldberg & Waage (1864): a chemical system

reaches a state in which a specic ra8o of reactant
and product concentraWons has a constant value.
The equilibrium constant expression for this reac8on
can be wriben

[C]c[D]d
Keq = a b
[A] [B]

The law of chemical equilibrium or the law of mass ac8on

Write the equilibrium constant expression for the following

reaction:

CH 4 (g) + 2H 2 S(g) CS2 (g) + 4H 2 (g)

Write the equilibrium constant expression for the following

reaction:

CH 4 (g) + 2H 2 S(g) CS2 (g) + 4H 2 (g)

[CH 4 ][H 2 S]2
A. K c =
[CS2 ][H 2 ]4

[CS2 ] [H 2 S]4
C. K c =
[CH 4 ] [H 2 ]2

[CH 4 ] [CS2 ]
B. K c =
[H 2 S]2 [H 2 ]4

[CS24 ] [H 2 ]4
D. K c =
[CH 4 ] [H 2 S]2

Write the equilibrium constant expression for the following

reaction:

CH 4 (g) + 2H 2 S(g) CS2 (g) + 4H 2 (g)

[CH 4 ][H 2 S]2
A. K c =
[CS2 ][H 2 ]4

[CS2 ] [H 2 S]4
C. K c =
[CH 4 ] [H 2 ]2

[CH 4 ] [CS2 ]
B. K c =
[H 2 S]2 [H 2 ]4

[CS24 ] [H 2 ]4
D. K c =
[CH 4 ] [H 2 S]2

Keq and the extent of reaction

K reflects a particular ratio of product concentrations to
reactant concentrations for a reaction.
K therefore indicates the extent of a reac8on, i.e., how far a
reac8on proceeds towards the products at a given
temperature.
A small value for K indicates that the reaction yields little
product before reaching equilibrium. The reaction favors
the reactants.
A large value for K indicates that the reaction reaches
equilibrium with very little reactant remaining. The
reaction favors the products.

CH3COOH(aq) + H2O(l) D H3O+(aq) + CH3COO(aq)

Keq = 1.8 x 105 at 25C
How far does the reaction proceed?
Is Keq large or small?
Given a solution of acetic acid, at equilibrium is there
more CH3COOH or more CH3COO ?

CH3COOH(aq) + H2O(l)
H3O+(aq) + CH3COO(aq)
Keq = 1.8 x 105 at 25C
How far does the reaction proceed?
Small value implies that equilibrium favors the
reactants. In 0.10 M CH3COOH(aq), 99% of acetic
acid is present as CH3COOH molecules.
Acetic acid is a weak acid because it is only
partially dissociated.

The Equilibrium Constant tells us the

extent of the reaction
2H2O(g)

2H2(g) + O2(g)

(at 500 K) Kc = 4.2 x 10-48

(at 500 K) Kc = 2.4 x 1047

H2(g) + I2(g)

2HI(g) Kc = 57.0
(at 700 K)

2H2(g) + O2(g)

2H2O(g)

Which of the following best describes a system at

equilibrium with a Kc of 5 x 104? A + B C + D
A. The system is nearing completion and will end soon
B. The reaction proceeds hardly at all, mostly reactants
present
C. Appreciable concentrations of both reactants and
products are present
D. There are mostly products present with some
reactants also present
E. The is no way to know from the information given

Which of the following best describes a system at

equilibrium with a Kc of 5 x 104? A + B C + D
A. The system is nearing completion and will end soon
B. The reaction proceeds hardly at all, mostly reactants
present
C. Appreciable concentrations of both reactants and
products are present
D. There are mostly products present with some
reactants also present
E. The is no way to know from the information given

H2(g) + I2(g) 2 HI(g)

At time 0 s, there are only reactants in the mixture.

Is this system at equilibrium?
[H2] = 8, [I2] = 8, [HI] = 0

H2(g) + I2(g) 2 HI(g)

At time 16 s, there are both reactants and products in the

mixture. Are both the forward reaction and reverse reaction
taking place? Is this system at equilibrium?
[H2] = 6, [I2] = 6, [HI] = 4

H2(g) + I2(g) 2 HI(g)

At time 32 s, do we have more products or more reactants

in the mixture? Which is now faster the forward reaction or
the reverse reaction? Is this system at equilibrium?
[H2] = 4, [I2] = 4, [HI] = 8

H2(g) + I2(g) 2 HI(g)

As the concentration of product increases and the
concentrations of reactants decrease, the rate of the forward
reaction slows down, and the rate of the reverse reaction speeds
up.

H2(g) + I2(g) 2 HI(g)

[H2] = 4, [I2] = 4, [HI] = 8

At time 48 s, the amounts of products and reactants in the

mixture havent changed. Are the forward and reverse
reactions are proceeding at the same rate? Has the system
reached equilibrium?

H2(g) + I2(g) 2 HI(g)

[H2] = 4, [I2] = 4, [HI] = 8

Assume [H2] = 4 M, etc.

Calculate Keq

H2(g) + I2(g) 2 HI(g)

[H2] = 4, [I2] = 4, [HI] = 8

Keq =

[8 M]2
= 4
=
[H2] [I2] [4 M] [4 M]
[HI]2

H2(g) + I2(g) 2 HI(g)

At dynamic equilibrium, the rate of the forward reaction is equal
to the rate of the reverse reaction.
The concentrations of reactants and products no longer change.

H2(g) + I2(g) 2 HI(g)

At dynamic equilibrium, the rate of the forward reaction is equal
to the rate of the reverse reaction.
The concentrations of reactants and products no longer change.
How do we determine when a system is NOT at equilibrium?

The Reaction Quotient, Q

For aqueous phase or gas phase reactions NOT at
equilibrium
aA + bB cC + dD
the reaction quotient is

The Reaction Quotient, Q

For the aqueous phase or gas phase reactions
NOT at equilibrium
aA + bB cC + dD
the reaction quotient is

Define quotient

The Reaction Quotient, Q

For the aqueous phase or gas phase reactions
NOT at equilibrium
aA + bB cC + dD
the reaction quotient is

Define quotient
In more abstract branches of mathema8cs, the word quo8ent is
o{en used to describe sets, spaces, or algebraic structures whose
elements are the equivalence classes of some equivalence
rela8on on another set, space, or algebraic structure.

The Reaction Quotient, Q

For the aqueous phase or gas phase reactions
NOT at equilibrium
aA + bB cC + dD
the reaction quotient is

Who is Q?

What is Q?

The Reaction Quotient, Q

For the aqueous phase or gas phase reactions
NOT at equilibrium
aA + bB cC + dD
the reaction quotient is

Who is Q?

What is Q?
What does Q have to do with Space &
Time?

The Reaction Quotient, Q

For the aqueous phase or gas phase reactions
aA + bB cC + dD
the reaction quotient is:

In mathema8cs, a quo8ent (from La8n: quo8ens)

is the result of division.

The value of Q, when compared to Keq, predicts if the system is

approaching equilibrium or is past equilibrium.

Reaction direction and the relative sizes of Q and K.

Q>K
Q<K

Q=K